CN109985618B - H occupies BiVO4-OVs photocatalytic material, preparation method and application thereof - Google Patents
H occupies BiVO4-OVs photocatalytic material, preparation method and application thereof Download PDFInfo
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- 230000001699 photocatalysis Effects 0.000 title claims abstract description 80
- 239000000463 material Substances 0.000 title claims abstract description 61
- 238000002360 preparation method Methods 0.000 title claims abstract description 9
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims abstract description 54
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 43
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 36
- 239000008367 deionised water Substances 0.000 claims abstract description 36
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 36
- 238000001354 calcination Methods 0.000 claims abstract description 25
- 238000000137 annealing Methods 0.000 claims abstract description 21
- 229910019501 NaVO3 Inorganic materials 0.000 claims abstract description 20
- CMZUMMUJMWNLFH-UHFFFAOYSA-N sodium metavanadate Chemical compound [Na+].[O-][V](=O)=O CMZUMMUJMWNLFH-UHFFFAOYSA-N 0.000 claims abstract description 20
- 239000002904 solvent Substances 0.000 claims abstract description 20
- 230000015572 biosynthetic process Effects 0.000 claims abstract description 18
- 238000001035 drying Methods 0.000 claims abstract description 18
- -1 polytetrafluoroethylene Polymers 0.000 claims abstract description 18
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims abstract description 18
- 239000004810 polytetrafluoroethylene Substances 0.000 claims abstract description 18
- 238000003786 synthesis reaction Methods 0.000 claims abstract description 18
- 238000005406 washing Methods 0.000 claims abstract description 18
- 238000002156 mixing Methods 0.000 claims abstract 2
- 238000004729 solvothermal method Methods 0.000 claims abstract 2
- 229910002915 BiVO4 Inorganic materials 0.000 claims description 40
- 239000003344 environmental pollutant Substances 0.000 claims description 36
- 231100000719 pollutant Toxicity 0.000 claims description 36
- 239000002243 precursor Substances 0.000 claims description 33
- 238000000034 method Methods 0.000 claims description 31
- 238000003756 stirring Methods 0.000 claims description 17
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 16
- 239000001301 oxygen Substances 0.000 claims description 16
- 229910052760 oxygen Inorganic materials 0.000 claims description 16
- 229910001868 water Inorganic materials 0.000 claims description 7
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 3
- 239000001257 hydrogen Substances 0.000 claims description 3
- 229910052739 hydrogen Inorganic materials 0.000 claims description 3
- 238000006722 reduction reaction Methods 0.000 claims 2
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims 1
- 229910000416 bismuth oxide Inorganic materials 0.000 claims 1
- TYIXMATWDRGMPF-UHFFFAOYSA-N dibismuth;oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Bi+3].[Bi+3] TYIXMATWDRGMPF-UHFFFAOYSA-N 0.000 claims 1
- 239000006185 dispersion Substances 0.000 claims 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims 1
- 238000013033 photocatalytic degradation reaction Methods 0.000 claims 1
- 229910052708 sodium Inorganic materials 0.000 claims 1
- 239000011734 sodium Substances 0.000 claims 1
- 239000000047 product Substances 0.000 abstract description 95
- 230000015556 catabolic process Effects 0.000 abstract description 22
- 238000006731 degradation reaction Methods 0.000 abstract description 22
- 230000007062 hydrolysis Effects 0.000 abstract description 3
- 238000006460 hydrolysis reaction Methods 0.000 abstract description 3
- 230000003197 catalytic effect Effects 0.000 abstract description 2
- 239000007795 chemical reaction product Substances 0.000 abstract 1
- 239000011259 mixed solution Substances 0.000 abstract 1
- 239000000243 solution Substances 0.000 abstract 1
- 239000003054 catalyst Substances 0.000 description 50
- 238000002835 absorbance Methods 0.000 description 34
- 239000011941 photocatalyst Substances 0.000 description 19
- 238000006243 chemical reaction Methods 0.000 description 17
- 238000005286 illumination Methods 0.000 description 16
- 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 description 16
- 229940043267 rhodamine b Drugs 0.000 description 16
- 238000001179 sorption measurement Methods 0.000 description 16
- 239000006228 supernatant Substances 0.000 description 16
- 238000001132 ultrasonic dispersion Methods 0.000 description 16
- 238000000870 ultraviolet spectroscopy Methods 0.000 description 16
- 238000012360 testing method Methods 0.000 description 15
- 230000031700 light absorption Effects 0.000 description 10
- 238000010521 absorption reaction Methods 0.000 description 9
- 238000002441 X-ray diffraction Methods 0.000 description 6
- 230000007547 defect Effects 0.000 description 5
- 230000003595 spectral effect Effects 0.000 description 5
- 238000001069 Raman spectroscopy Methods 0.000 description 4
- 238000005215 recombination Methods 0.000 description 4
- 230000006798 recombination Effects 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 3
- 238000001878 scanning electron micrograph Methods 0.000 description 3
- 230000009286 beneficial effect Effects 0.000 description 2
- PPNKDDZCLDMRHS-UHFFFAOYSA-N dinitrooxybismuthanyl nitrate Chemical compound [Bi+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O PPNKDDZCLDMRHS-UHFFFAOYSA-N 0.000 description 2
- 230000005264 electron capture Effects 0.000 description 2
- 238000006303 photolysis reaction Methods 0.000 description 2
- 230000015843 photosynthesis, light reaction Effects 0.000 description 2
- 238000006479 redox reaction Methods 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- 238000001392 ultraviolet--visible--near infrared spectroscopy Methods 0.000 description 2
- 239000013543 active substance Substances 0.000 description 1
- 229910052797 bismuth Inorganic materials 0.000 description 1
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 230000005284 excitation Effects 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 230000004298 light response Effects 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000007146 photocatalysis Methods 0.000 description 1
- 238000013032 photocatalytic reaction Methods 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- LSGOVYNHVSXFFJ-UHFFFAOYSA-N vanadate(3-) Chemical compound [O-][V]([O-])([O-])=O LSGOVYNHVSXFFJ-UHFFFAOYSA-N 0.000 description 1
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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
- B01J23/20—Vanadium, niobium or tantalum
- B01J23/22—Vanadium
-
- B01J35/39—
-
- 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
- C02F2305/00—Use of specific compounds during water treatment
- C02F2305/10—Photocatalysts
Abstract
Preparation of H-occupied BiVO4-OVs photocatalytic material and its use, the preparation method comprising: a certain molar amount of Bi (NO)3)3·5 H2Dissolving O in glycerol; a certain molar weight of NaVO3·2 H2Dissolving O in deionized water; mixing the above solutions; transferring the mixed solution into a high-pressure autoclave with a polytetrafluoroethylene lining, and keeping the temperature at 180 ℃ for 8 hours; centrifugally separating a solvent thermal synthesis product at 10000 rpm, washing with deionized water and ethanol, and drying at 60 ℃ for 4 hours; calcining the cleaned solvothermal reaction product in a muffle furnace at 300 ℃ for 5 hours; calcination of the product in Ar/H2Annealing at 350 ℃ for 10H in the atmosphere to obtain BiVO occupied by H4-OVs photocatalytic material. The invention has the advantages of wide photoresponse range, high catalytic activity, high degradation rate and strong hydrolysis capability, and can fully and effectively utilize solar energy.
Description
Technical Field
The invention relates to the technical field of photocatalytic materials, in particular to a method for preparing BiVO (BiVO) with H occupying oxygen-containing vacancy4(BiVO4OVs) photocatalytic material and its use.
Background
With the gradual aggravation of the problems of environmental pollution and energy shortage, the photocatalytic technology has the advantages of cleanness, environmental protection, low cost, huge energy and the like because sunlight is used as energy input, has huge influence on the aspects of hydrogen production by photolysis, pollutant degradation and the like, causes wide attention of scientists, and has good development prospect. However, the photocatalytic technology is still limited by two influencing factors, namely, the narrow spectral response range and the low quantum efficiency, so that how to broaden the spectral absorption, improve the solar energy utilization rate and inhibit the rapid recombination of the photo-generated electrons and holes becomes the core and the key of the current research.
Bismuth vanadate (BiVO)4) The forbidden band width of the organic hole is 2.3-2.4eV, the valence band position is high enough, and the degradation of the organic matters by the holes can be realized. The position of the conduction band is favorable for the reduction of photo-generated electrons, can decompose water and degrade pollutants under visible light, and the edge is very close to H2The evolution potential has the advantages of low initial potential, high photocurrent density and the like, and is considered to be one of the most promising Photoelectrochemical (PEC) water splitting photoanode materials. However, since the diffusion length of the carrier is short, the photo-generated electrons and holes are easily recombined, and the photoelectrocatalysis performance is reducedLow, becoming a limiting BiVO4Important factors for wide application.
Disclosure of Invention
In order to overcome the defects of the prior art, the invention aims to provide a method for preparing H-occupied BiVO4Method for preparing-OVs photocatalytic material and application thereof, H occupies BiVO4The OVs photocatalytic material has the advantages of reduced band gap, improved light absorption, widened light absorption range and excellent photocatalytic performance.
In order to achieve the purpose, the invention adopts the technical scheme that:
preparation of H-occupied BiVO4-method of OVs photocatalytic material comprising the steps of:
the method comprises the following steps:
a certain molar amount of Bi (NO)3)3·5 H2Dissolving O in glycerol to obtain a precursor solution A;
step two:
a certain molar weight of NaVO3·2 H2Dissolving O in deionized water to obtain a precursor solution B;
step three:
adding the solution A into the solution B and stirring vigorously to obtain a solution C;
step four:
transferring the solution C into a high-pressure autoclave with a polytetrafluoroethylene lining, and keeping the temperature at 180 ℃ for 8 hours to obtain a synthetic product D;
step five:
centrifuging and separating the solvent thermal synthesis product D at 10000 rpm, washing with deionized water and ethanol, and drying at 60 ℃ for 4 hours to obtain a product E;
step six:
calcining the product E in a muffle furnace at 300 ℃ for 5h to obtain a product F;
step seven:
product F at Ar/H2Annealing at 350 ℃ for 10H in the atmosphere to obtain BiVO occupied by H4-OVs photocatalytic material.
The temperature range of the solvent heat in the fourth step is 120-200 ℃.
And the solvent heat reaction time in the fourth step is 6-12 h.
The calcining temperature range in the sixth step is 250-450 ℃.
The calcining time range is 5-24 h.
The annealing temperature range in the seventh step is 300-400 ℃.
The annealing time range in the seventh step is 5-12 h.
Ar/H in the seventh step2The proportion range is 95%: 5% -70%: 30 percent.
H occupies BiVO4The OVs photocatalytic material is applied to photocatalytic technologies, such as pollutant degradation, photolysis of water and the like. A300W Xe lamp was used as a light source, and a cut-off filter with a wavelength of less than 800 nm was used to simulate sunlight. 50 ml of rhodamine B (Rh B) solution is measured, 20 ml of catalyst is added, and ultrasonic dispersion is carried out. Before illumination, the catalyst and the pollutants are adsorbed and stirred for 30 min in the dark to reach adsorption equilibrium. After turning on the lamp, 4 mL samples were taken from the reaction vessel at regular 20 min intervals. Separating the photocatalyst from the solution by using a 10000 r/min high-speed centrifuge for the sample taken out each time, taking the supernatant, measuring the absorbance of Rh B by using an ultraviolet-visible spectrophotometer, and judging the degradation efficiency of the catalyst to the pollutant solution according to the absorbance.
The invention has the beneficial effects that:
preparing BiVO occupied by H by adopting solvothermal-post annealing method4-OVs photocatalytic material. Oxygen vacancies in the composite material can absorb near infrared light, active sites are increased, and oxygen molecules are converted into active substances to participate in redox reaction; in BiVO4A defect state is formed below the conduction band, so that the forbidden bandwidth is reduced, and the light absorption range of the catalyst is improved; meanwhile, as a photo-generated electron capture center, the photo-generated electron capture center can effectively separate electron-hole pairs and transfer the electron-hole pairs to the surface of the catalyst under the excitation of long wavelength, inhibit the recombination of photo-generated electrons and holes, and improve the photocatalysis efficiency. In BiVO4Introduction of H into OVs2The valence band of the O vacancy occupied by H is used as a defect level or a shallow donor level, the band gap width is reduced, the light absorption range is enlarged, and the absorbance is obviously improved. Having electricity as photocatalytic materialHigh charge separation rate, wide light absorption range, high photocatalytic activity, high degradation rate and strong hydrolysis capacity.
Drawings
FIG. 1 shows that H occupies BiVO4-schematic representation of the preparation process of OVs photocatalytic material;
FIG. 2 shows that H occupies BiVO4-XRD patterns of OVs photocatalytic material;
FIG. 3 shows that H occupies BiVO4-SEM images of OVs photocatalytic material;
FIG. 4 shows that H occupies BiVO4-raman spectral images of OVs photocatalytic material;
FIG. 5 shows that H occupies BiVO4-uv-vis-nir absorption images of OVs photocatalytic materials.
Detailed Description
The present invention will be described in further detail with reference to the accompanying drawings.
Example 1
(1) 0.4 mmol of Bi (NO)3)3·5 H2Dissolving O in 16 ml of glycerol to obtain a precursor solution A;
(2) adding 0.4 mmol of NaVO3·2 H2Dissolving O in 16 ml of deionized water to obtain a precursor solution B;
(3) adding the solution A into the solution B and stirring vigorously to obtain a solution C;
(4) transferring the solution C into a high-pressure autoclave with a polytetrafluoroethylene lining, and keeping the temperature at 120 ℃ for 6 hours to obtain a synthetic product D;
(5) centrifuging and separating the solvent thermal synthesis product D at 10000 rpm, washing with deionized water and ethanol, and drying at 60 ℃ for 4 hours to obtain a product E;
(6) calcining the product E in a muffle furnace at 300 ℃ for 5h to obtain a product F;
(7) product F at Ar/H2Ar/H at 350 ℃ in an atmosphere2(Vol: 95%: 5%) annealing for 10H in an atmosphere to obtain BiVO occupied by H4-OVs photocatalytic material.
The obtained H occupies BiVO4The method for testing the photocatalytic performance of the OVs photocatalytic material is as follows:
A300W Xe lamp was used as a light source, and a cut-off filter with a wavelength of less than 800 nm was used to simulate sunlight. 50 ml of rhodamine B solution is measured, 20 ml of catalyst is added, and ultrasonic dispersion is carried out. Before illumination, the catalyst and the pollutants are adsorbed and stirred for 30 min in the dark to reach adsorption equilibrium. After turning on the lamp, 4 mL samples were taken from the reaction vessel at regular 20 min intervals. Separating the photocatalyst from the solution by using a 10000 r/min high-speed centrifuge for the sample taken out each time, taking the supernatant, measuring the absorbance of Rh B by using an ultraviolet-visible spectrophotometer, and judging the degradation efficiency of the catalyst to the pollutant solution according to the absorbance.
Example 2
(1) 0.4 mmol of Bi (NO)3)3·5 H2Dissolving O in 16 ml of glycerol to obtain a precursor solution A;
(2) adding 0.4 mmol of NaVO3·2 H2Dissolving O in 16 ml of deionized water to obtain a precursor solution B;
(3) adding the solution A into the solution B and stirring vigorously to obtain a solution C;
(4) transferring the solution C into a high-pressure autoclave with a polytetrafluoroethylene lining, and keeping the temperature at 180 ℃ for 8 hours to obtain a synthetic product D;
(5) centrifuging and separating the solvent thermal synthesis product D at 10000 rpm, washing with deionized water and ethanol, and drying at 60 ℃ for 4 hours to obtain a product E;
(6) calcining the product E in a muffle furnace at 300 ℃ for 5h to obtain a product F;
(7) product F at Ar/H2Ar/H at 350 ℃ in an atmosphere2(Vol: 95%: 5%) annealing for 10H in an atmosphere to obtain BiVO occupied by H4-OVs photocatalytic material.
The obtained H occupies BiVO4-OVs photocatalytic material, denoted OVH-BiVO4The method for testing the photocatalytic performance comprises the following steps:
A300W Xe lamp was used as a light source, and a cut-off filter with a wavelength of less than 800 nm was used to simulate sunlight. 50 ml of rhodamine B solution is measured, 20 ml of catalyst is added, and ultrasonic dispersion is carried out. Before illumination, the catalyst and the pollutants are adsorbed and stirred for 30 min in the dark to reach adsorption equilibrium. After turning on the lamp, 4 mL samples were taken from the reaction vessel at regular 20 min intervals. Separating the photocatalyst from the solution by using a 10000 r/min high-speed centrifuge for the sample taken out each time, taking the supernatant, measuring the absorbance of Rh B by using an ultraviolet-visible spectrophotometer, and judging the degradation efficiency of the catalyst to the pollutant solution according to the absorbance.
Example 3
(1) 0.4 mmol of Bi (NO)3)3·5 H2Dissolving O in 16 ml of glycerol to obtain a precursor solution A;
(2) adding 0.4 mmol of NaVO3·2 H2Dissolving O in 16 ml of deionized water to obtain a precursor solution B;
(3) adding the solution A into the solution B and stirring vigorously to obtain a solution C;
(4) transferring the solution C into a high-pressure autoclave with a polytetrafluoroethylene lining, and keeping the temperature at 180 ℃ for 10 hours to obtain a synthetic product D;
(5) centrifuging and separating the solvent thermal synthesis product D at 10000 rpm, washing with deionized water and ethanol, and drying at 60 ℃ for 4 hours to obtain a product E;
(6) calcining the product E in a muffle furnace at 300 ℃ for 5h to obtain a product F;
(7) product F at Ar/H2Ar/H at 350 ℃ in an atmosphere2(Vol: 95%: 5%) annealing for 10H in an atmosphere to obtain BiVO occupied by H4-OVs photocatalytic material.
The obtained H occupies BiVO4The method for testing the photocatalytic performance of the OVs photocatalytic material is as follows:
A300W Xe lamp was used as a light source, and a cut-off filter with a wavelength of less than 800 nm was used to simulate sunlight. 50 ml of rhodamine B solution is measured, 20 ml of catalyst is added, and ultrasonic dispersion is carried out. Before illumination, the catalyst and the pollutants are adsorbed and stirred for 30 min in the dark to reach adsorption equilibrium. After turning on the lamp, 4 mL samples were taken from the reaction vessel at regular 20 min intervals. Separating the photocatalyst from the solution by using a 10000 r/min high-speed centrifuge for the sample taken out each time, taking the supernatant, measuring the absorbance of Rh B by using an ultraviolet-visible spectrophotometer, and judging the degradation efficiency of the catalyst to the pollutant solution according to the absorbance.
Example 4
(1) Will be 0.4 mmol Bi(NO3)3·5 H2Dissolving O in 16 ml of glycerol to obtain a precursor solution A;
(2) adding 0.4 mmol of NaVO3·2 H2Dissolving O in 16 ml of deionized water to obtain a precursor solution B;
(3) adding the solution A into the solution B and stirring vigorously to obtain a solution C;
(4) transferring the solution C into a high-pressure autoclave with a polytetrafluoroethylene lining, and keeping the temperature at 200 ℃ for 12 hours to obtain a synthetic product D;
(5) centrifuging and separating the solvent thermal synthesis product D at 10000 rpm, washing with deionized water and ethanol, and drying at 60 ℃ for 4 hours to obtain a product E;
(6) calcining the product E in a muffle furnace at 300 ℃ for 5h to obtain a product F;
(7) product F at Ar/H2Ar/H at 350 ℃ in an atmosphere2(Vol: 95%: 5%) annealing for 10H in an atmosphere to obtain BiVO occupied by H4-OVs photocatalytic material.
The obtained H occupies BiVO4The method for testing the photocatalytic performance of the OVs photocatalytic material is as follows:
A300W Xe lamp was used as a light source, and a cut-off filter with a wavelength of less than 800 nm was used to simulate sunlight. 50 ml of rhodamine B solution is measured, 20 ml of catalyst is added, and ultrasonic dispersion is carried out. Before illumination, the catalyst and the pollutants are adsorbed and stirred for 30 min in the dark to reach adsorption equilibrium. After turning on the lamp, 4 mL samples were taken from the reaction vessel at regular 20 min intervals. Separating the photocatalyst from the solution by using a 10000 r/min high-speed centrifuge for the sample taken out each time, taking the supernatant, measuring the absorbance of Rh B by using an ultraviolet-visible spectrophotometer, and judging the degradation efficiency of the catalyst to the pollutant solution according to the absorbance.
Example 5
(1) 0.4 mmol of Bi (NO)3)3·5 H2Dissolving O in 16 ml of glycerol to obtain a precursor solution A;
(2) adding 0.4 mmol of NaVO3·2 H2Dissolving O in 16 ml of deionized water to obtain a precursor solution B;
(3) adding the solution A into the solution B and stirring vigorously to obtain a solution C;
(4) transferring the solution C into a high-pressure autoclave with a polytetrafluoroethylene lining, and keeping the temperature at 180 ℃ for 8 hours to obtain a synthetic product D;
(5) centrifuging and separating the solvent thermal synthesis product D at 10000 rpm, washing with deionized water and ethanol, and drying at 60 ℃ for 4 hours to obtain a product E;
(6) calcining the product E in a muffle furnace at 250 ℃ for 5h to obtain a product F;
(7) product F at Ar/H2Ar/H at 350 ℃ in an atmosphere2(Vol: 95%: 5%) annealing for 10H in an atmosphere to obtain BiVO occupied by H4-OVs photocatalytic material.
The obtained H occupies BiVO4The method for testing the photocatalytic performance of the OVs photocatalytic material is as follows:
A300W Xe lamp was used as a light source, and a cut-off filter with a wavelength of less than 800 nm was used to simulate sunlight. 50 ml of rhodamine B solution is measured, 20 ml of catalyst is added, and ultrasonic dispersion is carried out. Before illumination, the catalyst and the pollutants are adsorbed and stirred for 30 min in the dark to reach adsorption equilibrium. After turning on the lamp, 4 mL samples were taken from the reaction vessel at regular 20 min intervals. Separating the photocatalyst from the solution by using a 10000 r/min high-speed centrifuge for the sample taken out each time, taking the supernatant, measuring the absorbance of Rh B by using an ultraviolet-visible spectrophotometer, and judging the degradation efficiency of the catalyst to the pollutant solution according to the absorbance.
Example 6
(1) 0.4 mmol of Bi (NO)3)3·5 H2Dissolving O in 16 ml of glycerol to obtain a precursor solution A;
(2) adding 0.4 mmol of NaVO3·2 H2Dissolving O in 16 ml of deionized water to obtain a precursor solution B;
(3) adding the solution A into the solution B and stirring vigorously to obtain a solution C;
(4) transferring the solution C into a high-pressure autoclave with a polytetrafluoroethylene lining, and keeping the temperature at 180 ℃ for 8 hours to obtain a synthetic product D;
(5) centrifuging and separating the solvent thermal synthesis product D at 10000 rpm, washing with deionized water and ethanol, and drying at 60 ℃ for 4 hours to obtain a product E;
(6) calcining the product E in a muffle furnace at 300 ℃ for 5h to obtain a product F;
(7) product F at Ar/H2Ar/H at 350 ℃ in an atmosphere2(Vol: 95%: 5%) annealing for 10H in an atmosphere to obtain BiVO occupied by H4-OVs photocatalytic material.
The obtained H occupies BiVO4The method for testing the photocatalytic performance of the OVs photocatalytic material is as follows:
A300W Xe lamp was used as a light source, and a cut-off filter with a wavelength of less than 800 nm was used to simulate sunlight. 50 ml of rhodamine B solution is measured, 20 ml of catalyst is added, and ultrasonic dispersion is carried out. Before illumination, the catalyst and the pollutants are adsorbed and stirred for 30 min in the dark to reach adsorption equilibrium. After turning on the lamp, 4 mL samples were taken from the reaction vessel at regular 20 min intervals. Separating the photocatalyst from the solution by using a 10000 r/min high-speed centrifuge for the sample taken out each time, taking the supernatant, measuring the absorbance of Rh B by using an ultraviolet-visible spectrophotometer, and judging the degradation efficiency of the catalyst to the pollutant solution according to the absorbance.
Example 7
(1) 0.4 mmol of Bi (NO)3)3·5 H2Dissolving O in 16 ml of glycerol to obtain a precursor solution A;
(2) adding 0.4 mmol of NaVO3·2 H2Dissolving O in 16 ml of deionized water to obtain a precursor solution B;
(3) adding the solution A into the solution B and stirring vigorously to obtain a solution C;
(4) transferring the solution C into a high-pressure autoclave with a polytetrafluoroethylene lining, and keeping the temperature at 180 ℃ for 8 hours to obtain a synthetic product D;
(5) centrifuging and separating the solvent thermal synthesis product D at 10000 rpm, washing with deionized water and ethanol, and drying at 60 ℃ for 4 hours to obtain a product E;
(6) calcining the product E in a muffle furnace at 350 ℃ for 10 h to obtain a product F;
(7) product F at Ar/H2Ar/H at 350 ℃ in an atmosphere2(Vol: 95%: 5%) annealing for 10H in an atmosphere to obtain BiVO occupied by H4-OVs photocatalytic material.
The obtained H occupies BiVO4The method for testing the photocatalytic performance of the OVs photocatalytic material is as follows:
A300W Xe lamp was used as a light source, and a cut-off filter with a wavelength of less than 800 nm was used to simulate sunlight. 50 ml of rhodamine B solution is measured, 20 ml of catalyst is added, and ultrasonic dispersion is carried out. Before illumination, the catalyst and the pollutants are adsorbed and stirred for 30 min in the dark to reach adsorption equilibrium. After turning on the lamp, 4 mL samples were taken from the reaction vessel at regular 20 min intervals. Separating the photocatalyst from the solution by using a 10000 r/min high-speed centrifuge for the sample taken out each time, taking the supernatant, measuring the absorbance of Rh B by using an ultraviolet-visible spectrophotometer, and judging the degradation efficiency of the catalyst to the pollutant solution according to the absorbance.
Example 8
(1) 0.4 mmol of Bi (NO)3)3·5 H2Dissolving O in 16 ml of glycerol to obtain a precursor solution A;
(2) adding 0.4 mmol of NaVO3·2 H2Dissolving O in 16 ml of deionized water to obtain a precursor solution B;
(3) adding the solution A into the solution B and stirring vigorously to obtain a solution C;
(4) transferring the solution C into a high-pressure autoclave with a polytetrafluoroethylene lining, and keeping the temperature at 180 ℃ for 8 hours to obtain a synthetic product D;
(5) centrifuging and separating the solvent thermal synthesis product D at 10000 rpm, washing with deionized water and ethanol, and drying at 60 ℃ for 4 hours to obtain a product E;
(6) calcining the product E in a muffle furnace at 450 ℃ for 12h to obtain a product F;
(7) product F at Ar/H2Ar/H at 350 ℃ in an atmosphere2(Vol: 95%: 5%) annealing for 10H in an atmosphere to obtain BiVO occupied by H4-OVs photocatalytic material.
The obtained H occupies BiVO4The method for testing the photocatalytic performance of the OVs photocatalytic material is as follows:
A300W Xe lamp was used as a light source, and a cut-off filter with a wavelength of less than 800 nm was used to simulate sunlight. 50 ml of rhodamine B solution is measured, 20 ml of catalyst is added, and ultrasonic dispersion is carried out. Before illumination, the catalyst and the pollutants are adsorbed and stirred for 30 min in the dark to reach adsorption equilibrium. After turning on the lamp, 4 mL samples were taken from the reaction vessel at regular 20 min intervals. Separating the photocatalyst from the solution by using a 10000 r/min high-speed centrifuge for the sample taken out each time, taking the supernatant, measuring the absorbance of Rh B by using an ultraviolet-visible spectrophotometer, and judging the degradation efficiency of the catalyst to the pollutant solution according to the absorbance.
Example 9
(1) 0.4 mmol of Bi (NO)3)3·5 H2Dissolving O in 16 ml of glycerol to obtain a precursor solution A;
(2) adding 0.4 mmol of NaVO3·2 H2Dissolving O in 16 ml of deionized water to obtain a precursor solution B;
(3) adding the solution A into the solution B and stirring vigorously to obtain a solution C;
(4) transferring the solution C into a high-pressure autoclave with a polytetrafluoroethylene lining, and keeping the temperature at 180 ℃ for 8 hours to obtain a synthetic product D;
(5) centrifuging and separating the solvent thermal synthesis product D at 10000 rpm, washing with deionized water and ethanol, and drying at 60 ℃ for 4 hours to obtain a product E;
(6) calcining the product E in a muffle furnace at 300 ℃ for 5h to obtain a product F;
(7) product F at Ar/H2Ar/H at 300 ℃ in an atmosphere2(Vol: 95%: 5%) annealing for 5H in an atmosphere to obtain BiVO occupied by H4-OVs photocatalytic material.
The obtained H occupies BiVO4The method for testing the photocatalytic performance of the OVs photocatalytic material is as follows:
A300W Xe lamp was used as a light source, and a cut-off filter with a wavelength of less than 800 nm was used to simulate sunlight. 50 ml of rhodamine B solution is measured, 20 ml of catalyst is added, and ultrasonic dispersion is carried out. Before illumination, the catalyst and the pollutants are adsorbed and stirred for 30 min in the dark to reach adsorption equilibrium. After turning on the lamp, 4 mL samples were taken from the reaction vessel at regular 20 min intervals. Separating the photocatalyst from the solution by using a 10000 r/min high-speed centrifuge for the sample taken out each time, taking the supernatant, measuring the absorbance of Rh B by using an ultraviolet-visible spectrophotometer, and judging the degradation efficiency of the catalyst to the pollutant solution according to the absorbance.
Example 10
(1) 2.0 mmol of Bi (NO)3)3·5 H2Dissolving O in 16 ml of glycerol to obtain a precursor solution A;
(2) adding 0.4 mmol of NaVO3·2 H2Dissolving O in 16 ml of deionized water to obtain a precursor solution B;
(3) adding the solution A into the solution B and stirring vigorously to obtain a solution C;
(4) transferring the solution C into a high-pressure autoclave with a polytetrafluoroethylene lining, and keeping the temperature at 180 ℃ for 8 hours to obtain a synthetic product D;
(5) centrifuging and separating the solvent thermal synthesis product D at 10000 rpm, washing with deionized water and ethanol, and drying at 60 ℃ for 4 hours to obtain a product E;
(6) calcining the product E in a muffle furnace at 300 ℃ for 5h to obtain a product F;
(7) product F at Ar/H2Ar/H at 350 ℃ in an atmosphere2(Vol: 95%: 5%) annealing for 10H in an atmosphere to obtain BiVO occupied by H4-OVs photocatalytic material.
The obtained H occupies BiVO4The method for testing the photocatalytic performance of the OVs photocatalytic material is as follows:
A300W Xe lamp was used as a light source, and a cut-off filter with a wavelength of less than 800 nm was used to simulate sunlight. 50 ml of rhodamine B solution is measured, 20 ml of catalyst is added, and ultrasonic dispersion is carried out. Before illumination, the catalyst and the pollutants are adsorbed and stirred for 30 min in the dark to reach adsorption equilibrium. After turning on the lamp, 4 mL samples were taken from the reaction vessel at regular 20 min intervals. Separating the photocatalyst from the solution by using a 10000 r/min high-speed centrifuge for the sample taken out each time, taking the supernatant, measuring the absorbance of Rh B by using an ultraviolet-visible spectrophotometer, and judging the degradation efficiency of the catalyst to the pollutant solution according to the absorbance.
Example 11
(1) 1.2mmol of Bi (NO)3)3·5 H2Dissolving O in 16 ml of glycerol to obtain a precursor solution A;
(2) adding 0.4 mmol of NaVO3·2 H2O is dissolved in 16 ml of deionized water to obtainPrecursor solution B;
(3) adding the solution A into the solution B and stirring vigorously to obtain a solution C;
(4) transferring the solution C into a high-pressure autoclave with a polytetrafluoroethylene lining, and keeping the temperature at 180 ℃ for 8 hours to obtain a synthetic product D;
(5) centrifuging and separating the solvent thermal synthesis product D at 10000 rpm, washing with deionized water and ethanol, and drying at 60 ℃ for 4 hours to obtain a product E;
(6) calcining the product E in a muffle furnace at 300 ℃ for 5h to obtain a product F;
(7) product F at Ar/H2Ar/H at 400 ℃ in an atmosphere2(Vol: 90%: 10%) annealing for 12H in an atmosphere to obtain BiVO occupied by H4-OVs photocatalytic material.
The obtained H occupies BiVO4The method for testing the photocatalytic performance of the OVs photocatalytic material is as follows:
A300W Xe lamp was used as a light source, and a cut-off filter with a wavelength of less than 800 nm was used to simulate sunlight. 50 ml of rhodamine B solution is measured, 20 ml of catalyst is added, and ultrasonic dispersion is carried out. Before illumination, the catalyst and the pollutants are adsorbed and stirred for 30 min in the dark to reach adsorption equilibrium. After turning on the lamp, 4 mL samples were taken from the reaction vessel at regular 20 min intervals. Separating the photocatalyst from the solution by using a 10000 r/min high-speed centrifuge for the sample taken out each time, taking the supernatant, measuring the absorbance of Rh B by using an ultraviolet-visible spectrophotometer, and judging the degradation efficiency of the catalyst to the pollutant solution according to the absorbance.
Example 12
(1) 0.4 mmol of Bi (NO)3)3·5 H2Dissolving O in 16 ml of glycerol to obtain a precursor solution A;
(2) adding 0.4 mmol of NaVO3·2 H2Dissolving O in 16 ml of deionized water to obtain a precursor solution B;
(3) adding the solution A into the solution B and stirring vigorously to obtain a solution C;
(4) transferring the solution C into a high-pressure autoclave with a polytetrafluoroethylene lining, and keeping the temperature at 180 ℃ for 8 hours to obtain a synthetic product D;
(5) centrifuging and separating the solvent thermal synthesis product D at 10000 rpm, washing with deionized water and ethanol, and drying at 60 ℃ for 4 hours to obtain a product E;
(6) calcining the product E in a muffle furnace at 300 ℃ for 5h to obtain a product F;
(7) product F at Ar/H2Ar/H at 350 ℃ in an atmosphere2(Vol: 80%: 20%) annealing for 10H in an atmosphere to obtain a BiVO occupied by H4-OVs photocatalytic material.
The obtained H occupies BiVO4The method for testing the photocatalytic performance of the OVs photocatalytic material is as follows:
A300W Xe lamp was used as a light source, and a cut-off filter with a wavelength of less than 800 nm was used to simulate sunlight. 50 ml of rhodamine B solution is measured, 20 ml of catalyst is added, and ultrasonic dispersion is carried out. Before illumination, the catalyst and the pollutants are adsorbed and stirred for 30 min in the dark to reach adsorption equilibrium. After turning on the lamp, 4 mL samples were taken from the reaction vessel at regular 20 min intervals. Separating the photocatalyst from the solution by using a 10000 r/min high-speed centrifuge for the sample taken out each time, taking the supernatant, measuring the absorbance of Rh B by using an ultraviolet-visible spectrophotometer, and judging the degradation efficiency of the catalyst to the pollutant solution according to the absorbance.
Example 13
(1) 0.4 mmol of Bi (NO)3)3·5 H2Dissolving O in 16 ml of glycerol to obtain a precursor solution A;
(2) adding 0.4 mmol of NaVO3·2 H2Dissolving O in 16 ml of deionized water to obtain a precursor solution B;
(3) adding the solution A into the solution B and stirring vigorously to obtain a solution C;
(4) transferring the solution C into a high-pressure autoclave with a polytetrafluoroethylene lining, and keeping the temperature at 180 ℃ for 8 hours to obtain a synthetic product D;
(5) centrifuging and separating the solvent thermal synthesis product D at 10000 rpm, washing with deionized water and ethanol, and drying at 60 ℃ for 4 hours to obtain a product E;
the product E obtained was not calcined in a muffle furnace and not in Ar/H2Annealing in a reducing atmosphere, denoted OV' -BiVO4The method for testing the photocatalytic performance comprises the following steps:
A300W Xe lamp was used as a light source, and a cut-off filter with a wavelength of less than 800 nm was used to simulate sunlight. 50 ml of rhodamine B solution is measured, 20 ml of catalyst is added, and ultrasonic dispersion is carried out. Before illumination, the catalyst and the pollutants are adsorbed and stirred for 30 min in the dark to reach adsorption equilibrium. After turning on the lamp, 4 mL samples were taken from the reaction vessel at regular 20 min intervals. Separating the photocatalyst from the solution by using a 10000 r/min high-speed centrifuge for the sample taken out each time, taking the supernatant, measuring the absorbance of Rh B by using an ultraviolet-visible spectrophotometer, and judging the degradation efficiency of the catalyst to the pollutant solution according to the absorbance.
Example 14
(1) 0.4 mmol of Bi (NO)3)3·5 H2Dissolving O in 16 ml of glycerol to obtain a precursor solution A;
(2) adding 0.4 mmol of NaVO3·2 H2Dissolving O in 16 ml of deionized water to obtain a precursor solution B;
(3) adding the solution A into the solution B and stirring vigorously to obtain a solution C;
(4) transferring the solution C into a high-pressure autoclave with a polytetrafluoroethylene lining, and keeping the temperature at 180 ℃ for 8 hours to obtain a synthetic product D;
(5) centrifuging and separating the solvent thermal synthesis product D at 10000 rpm, washing with deionized water and ethanol, and drying at 60 ℃ for 4 hours to obtain a product E;
(6) calcining the product E in a muffle furnace at 300 ℃ for 5h to obtain a product F;
the product F is not in Ar/H2Annealing in a reducing atmosphere, denoted OV-BiVO4The method for testing the photocatalytic performance comprises the following steps:
A300W Xe lamp was used as a light source, and a cut-off filter with a wavelength of less than 800 nm was used to simulate sunlight. 50 ml of rhodamine B solution is measured, 20 ml of catalyst is added, and ultrasonic dispersion is carried out. Before illumination, the catalyst and the pollutants are adsorbed and stirred for 30 min in the dark to reach adsorption equilibrium. After turning on the lamp, 4 mL samples were taken from the reaction vessel at regular 20 min intervals. Separating the photocatalyst from the solution by using a 10000 r/min high-speed centrifuge for the sample taken out each time, taking the supernatant, measuring the absorbance of Rh B by using an ultraviolet-visible spectrophotometer, and judging the degradation efficiency of the catalyst to the pollutant solution according to the absorbance.
Example 15
(1) 0.4 mmol of Bi (NO)3)3·5 H2Dissolving O in 16 ml of glycerol to obtain a precursor solution A;
(2) adding 0.4 mmol of NaVO3·2 H2Dissolving O in 16 ml of deionized water to obtain a precursor solution B;
(3) adding the solution A into the solution B and stirring vigorously to obtain a solution C;
(4) transferring the solution C into a high-pressure autoclave with a polytetrafluoroethylene lining, and keeping the temperature at 180 ℃ for 8 hours to obtain a synthetic product D;
(5) centrifuging and separating the solvent thermal synthesis product D at 10000 rpm, washing with deionized water and ethanol, and drying at 60 ℃ for 4 hours to obtain a product E;
(6) product E at Ar/H2Ar/H at 350 ℃ in an atmosphere2(Vol: 80%: 20%) annealing for 10H in an atmosphere to obtain a BiVO occupied by H4-OVs photocatalytic material.
The product E obtained, without calcination in a muffle furnace, is designated OVH'-BiVO4The method for testing the photocatalytic performance comprises the following steps:
A300W Xe lamp was used as a light source, and a cut-off filter with a wavelength of less than 800 nm was used to simulate sunlight. 50 ml of rhodamine B solution is measured, 20 ml of catalyst is added, and ultrasonic dispersion is carried out. Before illumination, the catalyst and the pollutants are adsorbed and stirred for 30 min in the dark to reach adsorption equilibrium. After turning on the lamp, 4 mL samples were taken from the reaction vessel at regular 20 min intervals. Separating the photocatalyst from the solution by using a 10000 r/min high-speed centrifuge for the sample taken out each time, taking the supernatant, measuring the absorbance of Rh B by using an ultraviolet-visible spectrophotometer, and judging the degradation efficiency of the catalyst to the pollutant solution according to the absorbance.
Referring to FIG. 2, FIG. 2 shows H occupying BiVO4XRD patterns of OVs photocatalytic material. In the figure: a. BiVO not added with H and not calcined by a muffle furnace4XRD patterns of the samples prepared in examples 13 and 14, b H-added BiVO, whether or not calcined in a muffle furnace4XRD patterns of the samples prepared in example 15 and example 2, c. BiVO before and after addition of H without muffle furnace calcination4XRD patterns of the samples prepared in examples 15 and 13, d. BiVO containing oxygen vacancy before and after addition of H after muffle furnace calcination4The XRD patterns of the samples prepared in example 2 and example 14.
Referring to FIG. 3, FIG. 3 shows that H occupies BiVO4SEM image of OVs photocatalytic Material, i.e. OV made in example 2H-BiVO4SEM images of photocatalytic materials; the appearance of a sample is obvious, the size of the sample is uniform, the radius size of the sample is about 500-600 nm, the sample is of a mulberry-shaped structure, the surface of the sample is rough, more reaction active sites are provided for photocatalytic reaction, and capture of photo-generated electrons is facilitated.
Referring to FIG. 4, FIG. 4 shows H occupying BiVO4Raman spectral images of OVs photocatalytic materials, i.e. the occupation of BiVO by H obtained in examples 2, 13, 14, 154-raman spectral images of OVs photocatalytic material; OV-BiVO with oxygen vacancy observable4Compare BiVO4The peaks are consistent and the peak is reduced, thus proving the existence of oxygen vacancy. Meanwhile, H occupies BiVO4-OVs, i.e. OVH-BiVO4Compared with OV-BiVO4The peak is significantly reduced, indicating that H partially or completely occupies the oxygen vacancies. The presence of oxygen vacancies can be demonstrated by raman spectroscopy and it can also be demonstrated that H is capable of partially or fully occupying oxygen vacancies.
Referring to FIG. 5, FIG. 5 shows H occupying BiVO4UV-VISCO NIR absorption patterns of OVs photocatalytic materials, i.e. the occupation of BiVO by H obtained in examples 2, 13, 14, 154-uv-vis-nir absorption images of OVs photocatalytic materials; BiVO can be observed from the figure4Obvious absorption is realized within 500 nm of visible light; OV-BiVO4Compared with BiVO4The red shift phenomenon occurs, the visible light absorption range is increased, and the oxygen vacancy is proved to be beneficial to expanding the light response range; without muffle furnace calcination, by H2Annealed OVH'-BiVO4Has absorption in the full spectrum range of 200-2500 nm, and the absorption rate reaches more than 0.4(ii) a Calcining in muffle furnace, and passing through H2Annealed OVH-BiVO4The absorption rate in the full spectrum range of 200-2500 nm can reach more than 0.9, the photocatalyst has a wider light absorption range and stronger light absorption capacity, and the photocatalytic activity is obviously improved.
From the above examples, it can be seen that the H-occupied BiVO prepared by the method of the present invention4The preparation method of the-OVs photocatalyst material has simple steps, and the prepared H occupies BiVO4The OVs photocatalyst material has the advantages of large photoresponse range and high carrier separation rate, has the advantages of high catalytic activity, high degradation rate and strong hydrolysis capacity as a photocatalytic material, and provides a new idea for efficient utilization of solar energy.
H occupies BiVO4OVs technique for solving BiVO4Provides opportunities for band gap problems and carrier recombination problems, coarse porous BiVO4The absorption of more electrons is facilitated to carry out redox reaction, and after oxygen vacancy defects are introduced, the oxygen vacancies absorb near infrared light, so that the light absorption range is enlarged, and the active sites are increased. H occupies O vacancy to generate new defect energy level or shallow donor energy level, the band gap width is reduced, the light absorption range is enlarged, the absorbance is greatly improved, and the photocatalytic activity is obviously improved. Preparation of H-occupied BiVO4the-OVs photocatalytic material is an effective method and a reliable way for solving the problems that the photocatalytic material has wider band gap, narrow photoresponse range and extremely easy recombination of electrons and holes.
Claims (8)
1. H occupies BiVO4-method for the preparation of photocatalytic materials for OVs, characterized in that it comprises the following steps:
BiVO (bismuth oxide) is added4Calcining for 5 to 24 hours at the temperature of between 250 and 450 ℃ to obtain BiVO containing oxygen vacancy4；
BiVO containing oxygen vacancy4Carrying out reduction reaction at 300-400 ℃ in hydrogen reduction atmosphere to obtain H-occupied BiVO4-photocatalytic material of OVs.
2. The method of claim 1, wherein the hydrogen reducing atmosphere is Ar: h2Volume ratio is 95%: 5% -70%: 30% Ar/H2And (4) mixing the atmosphere.
3. The method of claim 1, wherein the BiVO is4Obtained by a process comprising the steps of: will be dispersed with Bi (NO)3)3·5 H2O, and NaVO3·2 H2Carrying out solvothermal reaction on the O dispersion at 120-200 ℃ to obtain BiVO4。
4. The method of claim 3, wherein Bi (NO)3)3·5 H2O and NaVO3·2 H2The molar ratio of O is 1: 1-5: 1.
5. The method according to any one of claims 1 to 4, characterized by comprising the specific steps of:
1) adding Bi (NO)3)3·5 H2Dissolving O in glycerol to obtain a precursor solution A;
2) NaVO (sodium VO)3·2 H2Dissolving O in deionized water to obtain a precursor solution B;
3) adding the solution A into the solution B and stirring vigorously to obtain a solution C; bi (NO)3)3·5 H2O and NaVO3·2 H2The molar ratio of O is 1: 1-5: 1; the volume ratio of the solution A to the solution B is 1: 1-5: 1;
4) transferring the solution C into a high-pressure autoclave with a polytetrafluoroethylene lining, and keeping the temperature at 120-200 ℃ for 6-12 h to obtain a synthetic product D;
5) centrifuging and separating the solvent thermal synthesis product D at 10000 rpm, washing with deionized water and ethanol, and drying to obtain a product E;
6) calcining the product E in a muffle furnace at the temperature of 250-450 ℃ for 5-24 h to obtain a product F;
7) product F at Ar/H2Annealing for 5 to 12 hours at the temperature of between 300 and 400 ℃ in the atmosphere to obtain BiVO occupied by H4-OVs photocatalytic material; the Ar/H2Volume ratio is 95%: 5% -70%: 30 percent.
6. An H-occupied BiVO prepared by the process of any one of claims 1 to 54-photocatalytic material of OVs, characterized in that the hydrogen atoms partially or completely occupy BiVO containing oxygen vacancies4Oxygen vacancies in the structure.
7. The photocatalytic material of claim 6, characterized by a nano-scale mulberry-like morphology.
8. An H-occupied BiVO according to claim 6 or 74-use of photocatalytic material of OVs for photocatalytic degradation of pollutants.
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| CN110983362B (en) * | 2019-12-19 | 2021-05-28 | 湖南大学 | MOFs-coated OV-BiVO4Composite photo-anode and preparation method and application thereof |
| CN111330575A (en) * | 2020-03-25 | 2020-06-26 | 陕西科技大学 | Recoverable flexible Ag/BiVO4Cotton fabric composite photocatalytic material, preparation method and application thereof |
| CN111330568A (en) * | 2020-03-25 | 2020-06-26 | 陕西科技大学 | BiVO modified by carbon cloth loaded in-situ growth non-noble metal Bi4Flexible easily-recycled photocatalytic material, preparation method and application thereof |
| CN111330576A (en) * | 2020-03-25 | 2020-06-26 | 陕西科技大学 | Biomaterial-loaded bimetal Ag/BiVO4Bi flexible easily-recycled photocatalytic material, preparation method and application thereof |
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