CN112275301A - Flower-shaped Bi2S3Load Fe doped Bi2MoO6Preparation method and application of composite photocatalyst - Google Patents
Flower-shaped Bi2S3Load Fe doped Bi2MoO6Preparation method and application of composite photocatalyst Download PDFInfo
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- 239000011941 photocatalyst Substances 0.000 title claims abstract description 31
- 239000002131 composite material Substances 0.000 title claims abstract description 29
- 238000000034 method Methods 0.000 title claims description 11
- 229910002900 Bi2MoO6 Inorganic materials 0.000 claims abstract description 64
- 239000004005 microsphere Substances 0.000 claims abstract description 55
- 238000006243 chemical reaction Methods 0.000 claims description 58
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 40
- UMGDCJDMYOKAJW-UHFFFAOYSA-N thiourea Chemical compound NC(N)=S UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 claims description 30
- RXPAJWPEYBDXOG-UHFFFAOYSA-N hydron;methyl 4-methoxypyridine-2-carboxylate;chloride Chemical compound Cl.COC(=O)C1=CC(OC)=CC=N1 RXPAJWPEYBDXOG-UHFFFAOYSA-N 0.000 claims description 27
- 238000010438 heat treatment Methods 0.000 claims description 25
- VCJMYUPGQJHHFU-UHFFFAOYSA-N iron(3+);trinitrate Chemical compound [Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O VCJMYUPGQJHHFU-UHFFFAOYSA-N 0.000 claims description 22
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 20
- 229910052799 carbon Inorganic materials 0.000 claims description 19
- 239000002904 solvent Substances 0.000 claims description 19
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Natural products NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 15
- -1 polytetrafluoroethylene Polymers 0.000 claims description 15
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims description 15
- 239000004810 polytetrafluoroethylene Substances 0.000 claims description 15
- 238000003756 stirring Methods 0.000 claims description 15
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 claims description 11
- 239000008103 glucose Substances 0.000 claims description 11
- 238000009413 insulation Methods 0.000 claims description 11
- 235000015393 sodium molybdate Nutrition 0.000 claims description 10
- 239000011684 sodium molybdate Substances 0.000 claims description 10
- TVXXNOYZHKPKGW-UHFFFAOYSA-N sodium molybdate (anhydrous) Chemical compound [Na+].[Na+].[O-][Mo]([O-])(=O)=O TVXXNOYZHKPKGW-UHFFFAOYSA-N 0.000 claims description 10
- 239000012298 atmosphere Substances 0.000 claims description 9
- WQZGKKKJIJFFOK-VFUOTHLCSA-N beta-D-glucose Chemical compound OC[C@H]1O[C@@H](O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-VFUOTHLCSA-N 0.000 claims description 8
- 239000011248 coating agent Substances 0.000 claims description 8
- 238000000576 coating method Methods 0.000 claims description 8
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 claims description 8
- 238000004729 solvothermal method Methods 0.000 claims description 7
- 238000002360 preparation method Methods 0.000 claims description 6
- GSDSWSVVBLHKDQ-UHFFFAOYSA-N 9-fluoro-3-methyl-10-(4-methylpiperazin-1-yl)-7-oxo-2,3-dihydro-7H-[1,4]oxazino[2,3,4-ij]quinoline-6-carboxylic acid Chemical compound FC1=CC(C(C(C(O)=O)=C2)=O)=C3N2C(C)COC3=C1N1CCN(C)CC1 GSDSWSVVBLHKDQ-UHFFFAOYSA-N 0.000 abstract description 7
- 239000003242 anti bacterial agent Substances 0.000 abstract description 7
- 229940088710 antibiotic agent Drugs 0.000 abstract description 7
- 229960001699 ofloxacin Drugs 0.000 abstract description 7
- 238000013033 photocatalytic degradation reaction Methods 0.000 abstract description 7
- 230000006798 recombination Effects 0.000 abstract description 7
- 238000005215 recombination Methods 0.000 abstract description 7
- 230000000694 effects Effects 0.000 abstract description 6
- 230000002349 favourable effect Effects 0.000 abstract description 3
- 230000005540 biological transmission Effects 0.000 abstract description 2
- 239000012535 impurity Substances 0.000 abstract description 2
- 230000002401 inhibitory effect Effects 0.000 abstract description 2
- 239000002057 nanoflower Substances 0.000 abstract description 2
- 239000002086 nanomaterial Substances 0.000 abstract description 2
- 239000002073 nanorod Substances 0.000 abstract description 2
- 238000001338 self-assembly Methods 0.000 abstract 1
- 238000001816 cooling Methods 0.000 description 13
- 238000005406 washing Methods 0.000 description 13
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 8
- 238000000967 suction filtration Methods 0.000 description 7
- 239000012153 distilled water Substances 0.000 description 6
- 238000001914 filtration Methods 0.000 description 6
- 239000000243 solution Substances 0.000 description 6
- 238000001035 drying Methods 0.000 description 5
- 239000002351 wastewater Substances 0.000 description 3
- 238000003911 water pollution Methods 0.000 description 3
- 239000004098 Tetracycline Substances 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- 239000000969 carrier Substances 0.000 description 2
- 230000001699 photocatalysis Effects 0.000 description 2
- 229960002180 tetracycline Drugs 0.000 description 2
- 229930101283 tetracycline Natural products 0.000 description 2
- 235000019364 tetracycline Nutrition 0.000 description 2
- 150000003522 tetracyclines Chemical class 0.000 description 2
- WUPHOULIZUERAE-UHFFFAOYSA-N 3-(oxolan-2-yl)propanoic acid Chemical compound OC(=O)CCC1CCCO1 WUPHOULIZUERAE-UHFFFAOYSA-N 0.000 description 1
- 238000002835 absorbance Methods 0.000 description 1
- 239000012984 antibiotic solution Substances 0.000 description 1
- 238000009360 aquaculture Methods 0.000 description 1
- 244000144974 aquaculture Species 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000003115 biocidal effect Effects 0.000 description 1
- 238000006065 biodegradation reaction Methods 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
- 229910052980 cadmium sulfide Inorganic materials 0.000 description 1
- 239000004202 carbamide Substances 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 239000010840 domestic wastewater Substances 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- JMANVNJQNLATNU-UHFFFAOYSA-N oxalonitrile Chemical compound N#CC#N JMANVNJQNLATNU-UHFFFAOYSA-N 0.000 description 1
- 238000010525 oxidative degradation reaction Methods 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 238000007146 photocatalysis Methods 0.000 description 1
- 238000001782 photodegradation Methods 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 238000006479 redox reaction Methods 0.000 description 1
- 150000003384 small molecules Chemical class 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000009210 therapy by ultrasound Methods 0.000 description 1
- 239000004408 titanium dioxide Substances 0.000 description 1
- 238000000870 ultraviolet spectroscopy Methods 0.000 description 1
- 229910052724 xenon Inorganic materials 0.000 description 1
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 description 1
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- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/02—Sulfur, selenium or tellurium; Compounds thereof
- B01J27/04—Sulfides
- B01J27/047—Sulfides with chromium, molybdenum, tungsten or polonium
- B01J27/051—Molybdenum
- B01J27/0515—Molybdenum with iron group metals or platinum group metals
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Abstract
The invention relates to the technical field of photocatalytic degradation and discloses flower-shaped Bi2S3Load Fe doped Bi2MoO6Composite photocatalyst Fe doped Bi2MoO6The nano hollow microsphere has unique nano hollow appearance, higher specific surface area, more photochemical active sites on the surface and in the cavity, impurity energy level generated by Fe doping is favorable for inhibiting recombination of photo-generated electrons and holes, and Bi2S3The nano-rods form a flower-like nano structure by self-assembly, the specific surface area is large, and meanwhile, Bi is added2S3Nano flower and Fe doped Bi2MoO6The energy bands are matched, the two form a heterojunction structure, when light is radiated on the composite photocatalyst, a heterojunction carrier transmission mechanism is adopted, so that photogenerated electrons and holes in the heterojunction are effectively separated, the recombination and recombination phenomena are reduced, and the flower-shaped Bi is formed2S3Load Fe doped Bi2MoO6The composite photocatalyst has excellent photocatalytic degradation activity on ofloxacin antibiotics.
Description
Technical Field
The invention relates to the technical field of photocatalytic degradation, in particular to flower-shaped Bi2S3Load Fe doped Bi2MoO6A preparation method and application of the composite photocatalyst.
Background
In recent years, along with abuse of antibiotics such as tetracycline, ofloxacin and the like, a large amount of antibiotics are left in domestic wastewater, medical wastewater and aquaculture wastewater, the water body environment is seriously damaged and polluted, the health safety of aquatic organisms, growth and reproduction and human bodies is damaged, at present, the treatment method of the wastewater containing the antibiotics such as the ofloxacin and the like mainly comprises a physical adsorption method, an oxidative degradation method, a biodegradation method and the like, wherein photocatalytic degradation is a novel efficient water pollution treatment method, mainly, photo-generated carriers are generated on a photocatalyst through light irradiation and further react with water and oxygen to generate hydroxyl radicals and superoxide radicals with strong activity, and the photo-generated carriers and the active radicals can perform oxidation reduction reaction with the antibiotics such as the tetracycline, the ofloxacin and the like to degrade the antibiotics into small molecules which cannot be degraded.
The existing photocatalyst mainly comprises titanium dioxide, cadmium sulfide, graphite phase carbon nitride and the like, wherein bismuth-based compounds such as Bi2MoO6、BiOBr、Bi2WO6、Bi2S3The single Bi has good forbidden band width and photochemical activity and has wide research prospect in the field of photocatalysis2MoO6And Bi2S3The photo-generated electrons and holes are easy to recombine and seriously affectHas been influenced in photocatalytic activity and photodegradability, and Bi2MoO6And Bi2S3The heterojunction structure is constructed, so that the problem of recombination of photo-generated electrons and holes can be effectively solved.
Technical problem to be solved
Aiming at the defects of the prior art, the invention provides flower-shaped Bi2S3Load Fe doped Bi2MoO6The preparation method and the application of the composite photocatalyst solve the problem of single Bi2S3And Bi2MoO6The catalyst is easy to recombine the photo-generated electrons and holes.
(II) technical scheme
In order to achieve the purpose, the invention provides the following technical scheme: flower-shaped Bi2S3Load Fe doped Bi2MoO6The composite photocatalyst comprises: the flower-like Bi2S3Load Fe doped Bi2MoO6The preparation method of the composite photocatalyst comprises the following steps:
(1) adding an ethylene glycol solvent, glucose, bismuth nitrate, sodium molybdate and ferric nitrate into a conical flask, stirring for 1-3h, pouring the solution into a polytetrafluoroethylene reaction kettle, placing the reaction kettle in a reaction kettle heating device, carrying out solvothermal reaction, cooling, carrying out suction filtration, washing with distilled water and ethanol, and drying to obtain Fe-doped Bi2MoO6Coating the carbon nano-microspheres.
(2) Doping Fe with Bi2MoO6Placing the coated carbon nano-microspheres in a muffle furnace, and roasting to obtain Fe-doped Bi2MoO6Nano hollow microspheres.
(3) Adding glycol solvent and Fe doped Bi into a conical flask2MoO6Carrying out ultrasonic treatment on the nano hollow microspheres until the nano hollow microspheres are uniformly dispersed, then adding bismuth nitrate and thiourea, stirring for 1-2h, placing a conical flask in a microwave reactor, heating to 160 ℃ and 180 ℃, reacting for 1-2h, cooling, carrying out suction filtration and washing to obtain flower-shaped Bi2S3Load Fe doped Bi2MoO6The composite photocatalyst is applied to photocatalytic degradation and water pollution treatment.
Preferably, reation kettle heating device includes the insulating layer, and the inside reaction chamber that is provided with of insulating layer, reaction chamber below fixedly connected with heater, inside and bracing piece fixed connection of reaction chamber, cardboard in the bracing piece fixedly connected with all around, bracing piece and objective table fixed connection, the outer cardboard of objective table top fixedly connected with, the objective table top is provided with polytetrafluoroethylene reation kettle.
Preferably, the mass ratio of the glucose, the bismuth nitrate, the sodium molybdate and the ferric nitrate in the step (2) is 10:155-230:40-60: 8-20.
Preferably, the roasting process in the step (3) is an air atmosphere, and roasting is carried out at 350-400 ℃ for 2-4 h.
Preferably, the Fe in the step (4) is doped with Bi2MoO6The mass ratio of the nano hollow microspheres to the bismuth nitrate to the thiourea is 100:50-85: 24-42.
(III) advantageous technical effects
Compared with the prior art, the invention has the following chemical mechanism and beneficial technical effects:
the flower-shaped Bi2S3Load Fe doped Bi2MoO6The composite photocatalyst is prepared by using carbon nano-microspheres generated by a glucose hot solvent method as a hollow template agent and using ferric nitrate as Fe3+A source, in a thermal solvent system, generating a layer of Fe-doped Bi on the surface of the carbon nano microsphere in situ2MoO6Then removing the carbon nano microsphere template by air atmosphere baking to obtain Fe-doped Bi2MoO6The nano hollow microsphere has a unique nano hollow shape, has a higher specific surface area, contains more photochemical active sites on the surface and in the cavity, is favorable for improving the utilization rate of light radiation, and simultaneously, the impurity energy level generated by Fe doping is favorable for inhibiting the recombination of photo-generated electrons and holes, thereby improving the Fe-doped Bi2MoO6The photocatalytic activity of the hollow nano-microspheres.
The flower-shaped Bi2S3Load Fe doped Bi2MoO6The composite photocatalyst is prepared by doping Bi with Fe in a microwave thermal solvent system2MoO6Nano hollow microsphere as growth carrier, bismuth nitrate and sulfurFormation of Bi from urea2S3The nano-rods are self-assembled to form a flower-like nano-structure, the specific surface area is large, and meanwhile, Bi is added2S3Nano flower and Fe doped Bi2MoO6The energy bands are matched, the two form a heterojunction structure, when light is radiated on the composite photocatalyst, a heterojunction carrier transmission mechanism is adopted, so that photogenerated electrons and holes in the heterojunction are effectively separated, the recombination and recombination phenomena are reduced, and the flower-shaped Bi is formed2S3Load Fe doped Bi2MoO6The composite photocatalyst has excellent photocatalytic degradation activity on ofloxacin antibiotics.
Drawings
FIG. 1 is a schematic view of a heating apparatus of a reaction kettle;
fig. 2 is a schematic top view of the stage structure.
1-a reaction kettle heating device; 2-a heat insulation layer; 3-a reaction chamber; 4-a heater; 5-a support rod; 6-inner clamping plate; 7-an object stage; 8-outer snap-gauge; 9-polytetrafluoroethylene reaction kettle.
Detailed Description
To achieve the above object, the present invention provides the following embodiments and examples: flower-shaped Bi2S3Load Fe doped Bi2MoO6The preparation method of the composite photocatalyst comprises the following steps:
(1) adding ethylene glycol solvent, glucose, bismuth nitrate, sodium molybdate and ferric nitrate in a mass ratio of 10:155-2MoO6Coating the carbon nano-microspheres.
(2) Doping Fe with Bi2MoO6The coated carbon nano-microspheres are placed in a muffle furnace, and the roasting process is carried out for 2-4h at the temperature of 350-400 ℃ in the air atmosphere to obtain Fe doped Bi2MoO6Nano hollow microspheres.
(3) Adding glycol solvent and Fe doped Bi into a conical flask2MoO6Ultrasonically treating the nano hollow microspheres until the nano hollow microspheres are uniformly dispersed, and then adding bismuth nitrate and thiourea, wherein Fe is doped with Bi2MoO6Stirring the hollow nano-microspheres, bismuth nitrate and thiourea for 1-2 hours at a mass ratio of 100:50-85:24-42, placing the conical flask in a microwave reactor, heating to 160-180 ℃, reacting for 1-2 hours, cooling, filtering and washing to obtain flower-shaped Bi2S3Load Fe doped Bi2MoO6The composite photocatalyst is applied to photocatalytic degradation and water pollution treatment.
Example 1
(1) Adding ethylene glycol solvent, glucose, bismuth nitrate, sodium molybdate and ferric nitrate in a mass ratio of 10:155:40:8 into a conical flask, stirring for 1h, pouring the solution into a polytetrafluoroethylene reaction kettle, placing the reaction kettle in a reaction kettle heating device, wherein the reaction kettle heating device comprises a heat insulation layer, a reaction chamber is arranged in the heat insulation layer, a heater is fixedly connected below the reaction chamber, the interior of the reaction chamber is fixedly connected with a support rod, an inner clamping plate is fixedly connected around the support rod, the support rod is fixedly connected with an objective table, an outer clamping plate is fixedly connected above the objective table, the polytetrafluoroethylene reaction kettle is arranged above the objective table, carrying out solvothermal reaction, cooling, suction filtration, washing with distilled water and ethanol, and drying to obtain Fe-doped Bi2MoO6Coating the carbon nano-microspheres.
(2) Doping Fe with Bi2MoO6Placing the coated carbon nano-microspheres in a muffle furnace, and roasting at 350 ℃ for 2h in air atmosphere to obtain Fe-doped Bi2MoO6Nano hollow microspheres.
(3) Adding glycol solvent and Fe doped Bi into a conical flask2MoO6Ultrasonically treating the nano hollow microspheres until the nano hollow microspheres are uniformly dispersed, and then adding bismuth nitrate and thiourea, wherein Fe is doped with Bi2MoO6Preparation of nano hollow microsphere, bismuth nitrate and thioureaStirring for 1h with the mass ratio of 100:50:24, placing the conical flask in a microwave reactor, heating to 160 ℃, reacting for 1h, cooling, filtering and washing to obtain flower-shaped Bi2S3Load Fe doped Bi2MoO6A composite photocatalyst is provided.
Example 2
(1) Adding ethylene glycol solvent, glucose, bismuth nitrate, sodium molybdate and ferric nitrate in a mass ratio of 10:180:47:12 into a conical flask, stirring for 1h, pouring the solution into a polytetrafluoroethylene reaction kettle, placing the reaction kettle in a reaction kettle heating device, wherein the reaction kettle heating device comprises a heat insulation layer, a reaction chamber is arranged in the heat insulation layer, a heater is fixedly connected below the reaction chamber, the interior of the reaction chamber is fixedly connected with a support rod, an inner clamping plate is fixedly connected around the support rod, the support rod is fixedly connected with an objective table, an outer clamping plate is fixedly connected above the objective table, the polytetrafluoroethylene reaction kettle is arranged above the objective table, carrying out solvothermal reaction, cooling, suction filtration, washing with distilled water and ethanol, and drying to obtain Fe-doped Bi2MoO6Coating the carbon nano-microspheres.
(2) Doping Fe with Bi2MoO6Placing the coated carbon nano-microspheres in a muffle furnace, and roasting at 380 ℃ for 4h in air atmosphere to obtain Fe-doped Bi2MoO6Nano hollow microspheres.
(3) Adding glycol solvent and Fe doped Bi into a conical flask2MoO6Ultrasonically treating the nano hollow microspheres until the nano hollow microspheres are uniformly dispersed, and then adding bismuth nitrate and thiourea, wherein Fe is doped with Bi2MoO6Stirring the nano hollow microspheres, bismuth nitrate and thiourea for 2 hours at a mass ratio of 100:62:30, placing the conical flask in a microwave reactor, heating to 160 ℃, reacting for 1.5 hours, cooling, filtering and washing to obtain flower-shaped Bi2S3Load Fe doped Bi2MoO6A composite photocatalyst is provided.
Example 3
(1) Adding ethylene glycol solvent, glucose, bismuth nitrate, sodium molybdate and ferric nitrate in a mass ratio of 10:200:52:15 into a conical flask, stirring for 2h, pouring the solution into a polytetrafluoroethylene reaction kettle, placing the reaction kettle in a reaction kettle heating device, and heating the reaction kettle by using the reaction kettle heating deviceIncluding the insulating layer, the inside reaction chamber that is provided with of insulating layer, reaction chamber below fixedly connected with heater, inside and bracing piece fixed connection of reaction chamber, cardboard in the bracing piece fixedly connected with all around, bracing piece and objective table fixed connection, the outer cardboard of objective table top fixedly connected with, the objective table top is provided with polytetrafluoroethylene reation kettle, carries out the solvothermal reaction, cooling, suction filtration, distilled water and ethanol washing to it is dry, obtains Fe doping Bi2MoO6Coating the carbon nano-microspheres.
(2) Doping Fe with Bi2MoO6Placing the coated carbon nano-microspheres in a muffle furnace, and roasting at 380 ℃ for 3h in air atmosphere to obtain Fe-doped Bi2MoO6Nano hollow microspheres.
(3) Adding glycol solvent and Fe doped Bi into a conical flask2MoO6Ultrasonically treating the nano hollow microspheres until the nano hollow microspheres are uniformly dispersed, and then adding bismuth nitrate and thiourea, wherein Fe is doped with Bi2MoO6Stirring the nano hollow microspheres, bismuth nitrate and thiourea for 1.5h at a mass ratio of 100:75:37, placing the conical flask in a microwave reactor, heating to 170 ℃, reacting for 1.5h, cooling, filtering and washing to obtain flower-shaped Bi2S3Load Fe doped Bi2MoO6A composite photocatalyst is provided.
Example 4
(1) Adding ethylene glycol solvent, glucose, bismuth nitrate, sodium molybdate and ferric nitrate in a mass ratio of 10:230:60:20 into a conical flask, stirring for 3 hours, pouring the solution into a polytetrafluoroethylene reaction kettle, placing the reaction kettle in a reaction kettle heating device, wherein the reaction kettle heating device comprises a heat insulation layer, a reaction chamber is arranged in the heat insulation layer, a heater is fixedly connected below the reaction chamber, the interior of the reaction chamber is fixedly connected with a support rod, an inner clamping plate is fixedly connected around the support rod, the support rod is fixedly connected with an objective table, an outer clamping plate is fixedly connected above the objective table, the polytetrafluoroethylene reaction kettle is arranged above the objective table, carrying out solvothermal reaction, cooling, suction filtration, washing with distilled water and ethanol, and drying to obtain Fe-doped Bi2MoO6Coating the carbon nano-microspheres.
(2) Doping Fe with Bi2MoO6Placing the coated carbon nano-microspheres in a muffle furnace, and roasting at 400 ℃ for 4h in air atmosphere to obtain Fe-doped Bi2MoO6Nano hollow microspheres.
(3) Adding glycol solvent and Fe doped Bi into a conical flask2MoO6Ultrasonically treating the nano hollow microspheres until the nano hollow microspheres are uniformly dispersed, and then adding bismuth nitrate and thiourea, wherein Fe is doped with Bi2MoO6Stirring the nano hollow microspheres, bismuth nitrate and thiourea for 2 hours at a mass ratio of 100:85:42, placing the conical flask in a microwave reactor, heating to 180 ℃, reacting for 2 hours, cooling, filtering and washing to obtain flower-shaped Bi2S3Load Fe doped Bi2MoO6A composite photocatalyst is provided.
Comparative example 1
(1) Adding ethylene glycol solvent, glucose, bismuth nitrate, sodium molybdate and ferric nitrate in a mass ratio of 10:140:37:3 into a conical flask, stirring for 2 hours, pouring the solution into a polytetrafluoroethylene reaction kettle, placing the reaction kettle in a reaction kettle heating device, wherein the reaction kettle heating device comprises a heat insulation layer, a reaction chamber is arranged in the heat insulation layer, a heater is fixedly connected below the reaction chamber, the interior of the reaction chamber is fixedly connected with a support rod, an inner clamping plate is fixedly connected around the support rod, the support rod is fixedly connected with an objective table, an outer clamping plate is fixedly connected above the objective table, the polytetrafluoroethylene reaction kettle is arranged above the objective table, carrying out solvothermal reaction, cooling, suction filtration, washing with distilled water and ethanol, and drying to obtain Fe-doped Bi2MoO6Coating the carbon nano-microspheres.
(2) Doping Fe with Bi2MoO6Placing the coated carbon nano-microspheres in a muffle furnace, and roasting at 380 ℃ for 3h in air atmosphere to obtain Fe-doped Bi2MoO6Nano hollow microspheres.
(3) Adding glycol solvent and Fe doped Bi into a conical flask2MoO6Ultrasonically treating the nano hollow microspheres until the nano hollow microspheres are uniformly dispersed, and then adding bismuth nitrate and thiourea, wherein Fe is doped with Bi2MoO6The mass ratio of the nano hollow microspheres to the bismuth nitrate to the thiourea is 100:35:27, stirring for 2h, placing the conical flask in a microwave reactor, heating to 160 ℃, reacting for 1.5h,cooling, filtering and washing to obtain flower-shaped Bi2S3Load Fe doped Bi2MoO6A composite photocatalyst is provided.
Adding flower-shaped Bi into ofloxacin antibiotic solution with the concentration of 0.5 percent2S3Load Fe doped Bi2MoO6The concentration of the composite photocatalyst is controlled to be 5%, a 300W xenon lamp is used as a light source to irradiate and stir for 3h, a UV752N type ultraviolet-visible spectrophotometer is used for detecting the absorbance and the concentration of the ofloxacin antibiotic after the photodegradation, and the national standard of the detection is GB/T23762-.
Claims (5)
1. Flower-shaped Bi2S3Load Fe doped Bi2MoO6The composite photocatalyst is characterized in that: the flower-like Bi2S3Load Fe doped Bi2MoO6The preparation method of the composite photocatalyst is as follows:
(1) adding ethylene glycol solvent, glucose, bismuth nitrate, sodium molybdate and ferric nitrate into a conical flask, stirring for 1-3h, pouring the solution into a polytetrafluoroethylene reaction kettle, placing the reaction kettle in a heating device of the reaction kettle, and carrying out solvothermal reaction to obtain Fe-doped Bi2MoO6Coating carbon nano-microspheres;
(2) doping Fe with Bi2MoO6Placing the coated carbon nano-microspheres in a muffle furnace, and roasting to obtain Fe-doped Bi2MoO6Nano hollow microspheres;
(3) adding glycol solvent and Fe doped Bi into a conical flask2MoO6Ultrasonically treating the nano hollow microspheres until the nano hollow microspheres are uniformly dispersed, then adding bismuth nitrate and thiourea, stirring for 1-2h, placing the conical flask in a microwave reactor, heating to 160 ℃ and 180 ℃, and reacting for 1-2h to obtain flower-shaped Bi2S3Load Fe doped Bi2MoO6A composite photocatalyst is provided.
2. The flower-like Bi of claim 12S3Load Fe doped Bi2MoO6The composite photocatalyst is characterized in that: the reaction kettle heating device comprises a heat insulation layer, a reaction chamber is arranged inside the heat insulation layer, a heater is fixedly connected to the lower portion of the reaction chamber, the reaction chamber is fixedly connected with a support rod, an inner clamping plate is fixedly connected to the periphery of the support rod, the support rod is fixedly connected with an object stage, an outer clamping plate is fixedly connected to the upper portion of the object stage, and a polytetrafluoroethylene reaction kettle is arranged above the object stage.
3. The flower-like Bi of claim 12S3Load Fe doped Bi2MoO6The composite photocatalyst is characterized in that: the mass ratio of the glucose, the bismuth nitrate, the sodium molybdate and the ferric nitrate in the step (2) is 10:155-230:40-60: 8-20.
4. The flower-like Bi of claim 12S3Load Fe doped Bi2MoO6The composite photocatalyst is characterized in that: the roasting process in the step (3) is an air atmosphere, and roasting is carried out at the temperature of 350-400 ℃ for 2-4 h.
5. The flower-like Bi of claim 12S3Load Fe doped Bi2MoO6The composite photocatalyst is characterized in that: the Fe in the step (4) is doped with Bi2MoO6The mass ratio of the nano hollow microspheres to the bismuth nitrate to the thiourea is 100:50-85: 24-42.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US11084028B2 (en) * | 2018-11-15 | 2021-08-10 | Mohammad Haghighi Parapari | Semiconductor photocatalyst and preparation method thereof |
| CN115591559A (en) * | 2022-09-16 | 2023-01-13 | 武汉榆汐科技有限公司（Cn） | Preparation method of PtCu alloy ternary heterojunction photocatalyst, product and application thereof |
| CN115672353A (en) * | 2022-11-17 | 2023-02-03 | 昆明理工大学 | Bi 2 S 3 /Bi 2 WO 6 Heterojunction photocatalytic material and preparation method and application thereof |
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2020
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US11084028B2 (en) * | 2018-11-15 | 2021-08-10 | Mohammad Haghighi Parapari | Semiconductor photocatalyst and preparation method thereof |
| CN115591559A (en) * | 2022-09-16 | 2023-01-13 | 武汉榆汐科技有限公司（Cn） | Preparation method of PtCu alloy ternary heterojunction photocatalyst, product and application thereof |
| CN115672353A (en) * | 2022-11-17 | 2023-02-03 | 昆明理工大学 | Bi 2 S 3 /Bi 2 WO 6 Heterojunction photocatalytic material and preparation method and application thereof |
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