CN116493028A - Molybdenum oxide/bismuth oxybromide composite photocatalyst and preparation method thereof - Google Patents
Molybdenum oxide/bismuth oxybromide composite photocatalyst and preparation method thereof Download PDFInfo
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- CN116493028A CN116493028A CN202310471954.XA CN202310471954A CN116493028A CN 116493028 A CN116493028 A CN 116493028A CN 202310471954 A CN202310471954 A CN 202310471954A CN 116493028 A CN116493028 A CN 116493028A
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- 239000011941 photocatalyst Substances 0.000 title claims abstract description 42
- 239000002131 composite material Substances 0.000 title claims abstract description 21
- 229910000476 molybdenum oxide Inorganic materials 0.000 title claims abstract description 15
- PQQKPALAQIIWST-UHFFFAOYSA-N oxomolybdenum Chemical compound [Mo]=O PQQKPALAQIIWST-UHFFFAOYSA-N 0.000 title claims abstract description 15
- OZKCXDPUSFUPRJ-UHFFFAOYSA-N oxobismuth;hydrobromide Chemical compound Br.[Bi]=O OZKCXDPUSFUPRJ-UHFFFAOYSA-N 0.000 title claims abstract description 14
- 238000002360 preparation method Methods 0.000 title abstract description 15
- 239000007864 aqueous solution Substances 0.000 claims abstract description 32
- 229910052761 rare earth metal Inorganic materials 0.000 claims abstract description 19
- 238000000137 annealing Methods 0.000 claims abstract description 16
- 238000001027 hydrothermal synthesis Methods 0.000 claims abstract description 15
- FBPFZTCFMRRESA-KVTDHHQDSA-N D-Mannitol Chemical compound OC[C@@H](O)[C@@H](O)[C@H](O)[C@H](O)CO FBPFZTCFMRRESA-KVTDHHQDSA-N 0.000 claims abstract description 13
- 229930195725 Mannitol Natural products 0.000 claims abstract description 13
- 235000010355 mannitol Nutrition 0.000 claims abstract description 13
- 239000000594 mannitol Substances 0.000 claims abstract description 13
- 238000003756 stirring Methods 0.000 claims abstract description 12
- 238000001035 drying Methods 0.000 claims abstract description 11
- 238000005406 washing Methods 0.000 claims abstract description 11
- 238000000227 grinding Methods 0.000 claims abstract description 10
- 238000002156 mixing Methods 0.000 claims abstract description 10
- 239000002243 precursor Substances 0.000 claims abstract description 10
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 claims abstract description 9
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims abstract description 9
- 229910052797 bismuth Inorganic materials 0.000 claims abstract description 9
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 claims abstract description 9
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 claims abstract description 9
- 229910052794 bromium Inorganic materials 0.000 claims abstract description 9
- 229910052750 molybdenum Inorganic materials 0.000 claims abstract description 9
- 239000011733 molybdenum Substances 0.000 claims abstract description 9
- 239000002904 solvent Substances 0.000 claims abstract description 3
- 239000000243 solution Substances 0.000 claims description 24
- -1 rare earth ion Chemical class 0.000 claims description 22
- IOLCXVTUBQKXJR-UHFFFAOYSA-M potassium bromide Chemical compound [K+].[Br-] IOLCXVTUBQKXJR-UHFFFAOYSA-M 0.000 claims description 16
- 238000000034 method Methods 0.000 claims description 10
- 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 8
- JHJLBTNAGRQEKS-UHFFFAOYSA-M sodium bromide Chemical compound [Na+].[Br-] JHJLBTNAGRQEKS-UHFFFAOYSA-M 0.000 claims description 8
- 150000002500 ions Chemical class 0.000 claims description 7
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 4
- 229910000380 bismuth sulfate Inorganic materials 0.000 claims description 4
- 239000003054 catalyst Substances 0.000 claims description 4
- BEQZMQXCOWIHRY-UHFFFAOYSA-H dibismuth;trisulfate Chemical compound [Bi+3].[Bi+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O BEQZMQXCOWIHRY-UHFFFAOYSA-H 0.000 claims description 4
- 150000002910 rare earth metals Chemical class 0.000 claims description 4
- POILWHVDKZOXJZ-ARJAWSKDSA-M (z)-4-oxopent-2-en-2-olate Chemical compound C\C([O-])=C\C(C)=O POILWHVDKZOXJZ-ARJAWSKDSA-M 0.000 claims description 2
- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 claims description 2
- 229910002651 NO3 Inorganic materials 0.000 claims description 2
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 2
- 229910052769 Ytterbium Inorganic materials 0.000 claims description 2
- SWLVFNYSXGMGBS-UHFFFAOYSA-N ammonium bromide Chemical compound [NH4+].[Br-] SWLVFNYSXGMGBS-UHFFFAOYSA-N 0.000 claims description 2
- APUPEJJSWDHEBO-UHFFFAOYSA-P ammonium molybdate Chemical compound [NH4+].[NH4+].[O-][Mo]([O-])(=O)=O APUPEJJSWDHEBO-UHFFFAOYSA-P 0.000 claims description 2
- 229940010552 ammonium molybdate Drugs 0.000 claims description 2
- 235000018660 ammonium molybdate Nutrition 0.000 claims description 2
- 239000011609 ammonium molybdate Substances 0.000 claims description 2
- 229940036348 bismuth carbonate Drugs 0.000 claims description 2
- WMWLMWRWZQELOS-UHFFFAOYSA-N bismuth(III) oxide Inorganic materials O=[Bi]O[Bi]=O WMWLMWRWZQELOS-UHFFFAOYSA-N 0.000 claims description 2
- SFOQXWSZZPWNCL-UHFFFAOYSA-K bismuth;phosphate Chemical compound [Bi+3].[O-]P([O-])([O-])=O SFOQXWSZZPWNCL-UHFFFAOYSA-K 0.000 claims description 2
- 229910001622 calcium bromide Inorganic materials 0.000 claims description 2
- WGEFECGEFUFIQW-UHFFFAOYSA-L calcium dibromide Chemical compound [Ca+2].[Br-].[Br-] WGEFECGEFUFIQW-UHFFFAOYSA-L 0.000 claims description 2
- GMZOPRQQINFLPQ-UHFFFAOYSA-H dibismuth;tricarbonate Chemical compound [Bi+3].[Bi+3].[O-]C([O-])=O.[O-]C([O-])=O.[O-]C([O-])=O GMZOPRQQINFLPQ-UHFFFAOYSA-H 0.000 claims description 2
- 239000000203 mixture Substances 0.000 claims description 2
- 230000035484 reaction time Effects 0.000 claims description 2
- 239000000126 substance Substances 0.000 claims description 2
- 238000006243 chemical reaction Methods 0.000 abstract description 27
- 230000000694 effects Effects 0.000 abstract description 8
- 239000000463 material Substances 0.000 abstract description 7
- 238000000926 separation method Methods 0.000 abstract description 7
- 230000003197 catalytic effect Effects 0.000 abstract description 6
- 239000003344 environmental pollutant Substances 0.000 abstract description 6
- 231100000719 pollutant Toxicity 0.000 abstract description 6
- 238000013033 photocatalytic degradation reaction Methods 0.000 abstract description 4
- 239000003242 anti bacterial agent Substances 0.000 abstract description 3
- 229940088710 antibiotic agent Drugs 0.000 abstract description 3
- 230000015556 catabolic process Effects 0.000 abstract description 3
- 238000006731 degradation reaction Methods 0.000 abstract description 3
- 230000003115 biocidal effect Effects 0.000 abstract description 2
- 238000011031 large-scale manufacturing process Methods 0.000 abstract description 2
- 238000006555 catalytic reaction Methods 0.000 abstract 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 16
- 239000011259 mixed solution Substances 0.000 description 16
- 239000002244 precipitate Substances 0.000 description 16
- 238000001816 cooling Methods 0.000 description 15
- 230000001699 photocatalysis Effects 0.000 description 11
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 8
- 239000004810 polytetrafluoroethylene Substances 0.000 description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 7
- YBYGDBANBWOYIF-UHFFFAOYSA-N erbium(3+);trinitrate Chemical compound [Er+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O YBYGDBANBWOYIF-UHFFFAOYSA-N 0.000 description 7
- 238000011160 research Methods 0.000 description 7
- KUBYTSCYMRPPAG-UHFFFAOYSA-N ytterbium(3+);trinitrate Chemical compound [Yb+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O KUBYTSCYMRPPAG-UHFFFAOYSA-N 0.000 description 7
- 239000004065 semiconductor Substances 0.000 description 5
- 238000011161 development Methods 0.000 description 4
- 238000002198 surface plasmon resonance spectroscopy Methods 0.000 description 4
- 229910000510 noble metal Inorganic materials 0.000 description 3
- 239000000969 carrier Substances 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 238000003912 environmental pollution Methods 0.000 description 2
- 238000005215 recombination Methods 0.000 description 2
- 230000006798 recombination Effects 0.000 description 2
- 230000003595 spectral effect Effects 0.000 description 2
- 238000012546 transfer Methods 0.000 description 2
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 238000000862 absorption spectrum Methods 0.000 description 1
- 238000003916 acid precipitation Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 230000008878 coupling Effects 0.000 description 1
- 238000010168 coupling process Methods 0.000 description 1
- 238000005859 coupling reaction Methods 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- WDVGLADRSBQDDY-UHFFFAOYSA-N holmium(3+);trinitrate Chemical compound [Ho+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O WDVGLADRSBQDDY-UHFFFAOYSA-N 0.000 description 1
- 230000031700 light absorption Effects 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 230000005389 magnetism Effects 0.000 description 1
- 239000002906 medical waste Substances 0.000 description 1
- 238000007146 photocatalysis Methods 0.000 description 1
- 239000010865 sewage Substances 0.000 description 1
- LLZBVBSJCNUKLL-UHFFFAOYSA-N thulium(3+);trinitrate Chemical compound [Tm+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O LLZBVBSJCNUKLL-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
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/06—Halogens; Compounds thereof
- B01J27/132—Halogens; Compounds thereof with chromium, molybdenum, tungsten or polonium
-
- A—HUMAN NECESSITIES
- A62—LIFE-SAVING; FIRE-FIGHTING
- A62D—CHEMICAL MEANS FOR EXTINGUISHING FIRES OR FOR COMBATING OR PROTECTING AGAINST HARMFUL CHEMICAL AGENTS; CHEMICAL MATERIALS FOR USE IN BREATHING APPARATUS
- A62D3/00—Processes for making harmful chemical substances harmless or less harmful, by effecting a chemical change in the substances
- A62D3/10—Processes for making harmful chemical substances harmless or less harmful, by effecting a chemical change in the substances by subjecting to electric or wave energy or particle or ionizing radiation
- A62D3/17—Processes for making harmful chemical substances harmless or less harmful, by effecting a chemical change in the substances by subjecting to electric or wave energy or particle or ionizing radiation to electromagnetic radiation, e.g. emitted by a laser
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- B01J35/39—
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- 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
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- A—HUMAN NECESSITIES
- A62—LIFE-SAVING; FIRE-FIGHTING
- A62D—CHEMICAL MEANS FOR EXTINGUISHING FIRES OR FOR COMBATING OR PROTECTING AGAINST HARMFUL CHEMICAL AGENTS; CHEMICAL MATERIALS FOR USE IN BREATHING APPARATUS
- A62D2101/00—Harmful chemical substances made harmless, or less harmful, by effecting chemical change
- A62D2101/20—Organic substances
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- 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
-
- 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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- 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
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W10/00—Technologies for wastewater treatment
- Y02W10/30—Wastewater or sewage treatment systems using renewable energies
- Y02W10/37—Wastewater or sewage treatment systems using renewable energies using solar energy
Abstract
The invention discloses a molybdenum oxide/bismuth oxybromide composite photocatalyst and a preparation method thereof, and is characterized by comprising the following steps: dissolving a bismuth source and a rare earth ion source in a mannitol solvent, stirring and mixing uniformly, adding an aqueous solution containing a bromine source, performing hydrothermal reaction on the obtained aqueous solution, centrifuging, washing and drying to obtain a BiOBr: RE precursor; adjusting the ratio of BiOBr to RE and molybdenum source, fully grinding, stirring, and annealing to obtain MoO 3‑x BiOBr: RE composite photocatalyst. The invention has excellent catalytic degradation effect on antibiotics and organic dye pollutants, and has lightThe raw carrier separation efficiency is high, the near infrared light can be effectively utilized, and the catalysis efficiency is high; the material has low preparation difficulty, mild reaction condition and low cost, is suitable for large-scale production, and is a novel and efficient material for photocatalytic degradation of antibiotic pollutants.
Description
Technical Field
The invention belongs to the technical field of photocatalytic materials, and particularly relates to a molybdenum oxide/bismuth oxybromide composite photocatalyst and a preparation method thereof.
Background
With the rapid development of global technology and economy, the use amount of traditional fossil energy is continuously increased, and the random discharge of factory sewage and medical waste is caused, so that the problems of energy shortage and environmental pollution are increasingly serious. Furthermore, the large amounts of CO released from fossil energy use 2 Isothermal chamber gases raise a range of environmental and ecological problems such as greenhouse effect, acid rain, etc. Therefore, solving the energy shortage and environmental pollution has become a focus of attention of countries around the world. The development of renewable energy sources to sustain the sustainable development of today's society is a challenge facing the current international scientific research and is also an important strategic goal of development in countries around the world.
BiOBr, as a layered semiconductor, has good properties in terms of optics, electricity, magnetism, photocatalysis, etc., and thus has attracted extensive attention and research. However, the photocatalytic efficiency is limited due to the narrow spectral response range and the easy recombination of photo-generated electron-hole pairs. Therefore, developing a bilbr-based composite material with high photogenerated carrier separation efficiency, broad spectral response, low cost remains a great interest and challenge.
In recent years, rare earth ion doping has become an improvement in photocatalytic performance of semiconductor materialsOne of the effective ways. Research shows that rare earth ion doped can provide shallow trap for photo-generated electron, raise electron separation and carrier transfer efficiency and lower electron-hole pair recombination probability. However, the narrow range of photo-response remains one of the key factors limiting its photocatalytic efficiency. The construction of heterojunction by coupling noble metals (such as Au, ag, pt, etc.) with near-infrared Surface Plasmon Resonance (SPR) effect with semiconductors is an effective means to expand the photoresponse range and improve the charge separation efficiency at the same time, but its expensive cost greatly limits its practical application. Recently, research has found MoO 3-x Also shows the SPR effect similar to noble metal and is expected to become a substitute for noble metal surface plasma. Orthogonal phase molybdenum oxide is considered to be one of the most promising semiconductor materials for lithium batteries, sensors, light emitting diodes and photocatalysts due to its unique layered structure and environmental friendliness. MoO in recent years 3-x Constructing heterojunction is used for photocatalytic degradation of pollutants, but less research is applied to near-infrared surface plasmon resonance effect of the heterojunction, and MoO is not utilized 3-x The excellent near infrared absorption capability results in limited improvement of photocatalytic activity. Thus, new methods have been developed to synthesize MoO 3-x The BiOBr: RE composite photocatalyst has better research significance and research value for developing Bi-based photocatalytic materials and application thereof.
Accordingly, in order to solve the above problems, a molybdenum oxide/bismuth oxybromide composite photocatalyst and a method for preparing the same are proposed herein.
Disclosure of Invention
In order to solve the technical problems, the invention designs a molybdenum oxide/bismuth oxybromide composite photocatalyst and a preparation method thereof, and the MoO prepared by the invention 3-x The RE heterojunction photocatalyst has excellent catalytic degradation effect on antibiotics and organic dye pollutants, and has the advantages of high separation efficiency of photogenerated carriers, effective utilization of near infrared light and high catalytic efficiency.
In order to achieve the technical effects, the invention is realized by the following technical scheme: a composite photocatalyst is characterized in that,the chemical formula of the catalyst is as follows: moO (MoO) 3-x /BiOBr:RE。
Another object of the present invention is to provide a method for preparing a composite photocatalyst, which is characterized by comprising the steps of:
step1: dissolving a bismuth source and a rare earth ion source in a mannitol solvent, stirring and mixing uniformly, adding an aqueous solution containing a bromine source, performing hydrothermal reaction on the obtained aqueous solution, centrifuging, washing and drying to obtain a BiOBr: RE precursor;
step2: adjusting the proportion of BiOBr, RE and a molybdenum source, and fully grinding and stirring;
step3: annealing the mixture obtained in Step2 to obtain MoO 3-x BiOBr: RE composite photocatalyst.
Further, the volume ratio of the bismuth source to the mannitol solution is 0.1-3 g:20-50 mL; the bismuth source is one or more of bismuth nitrate pentahydrate, bismuth carbonate, bismuth phosphate, bismuth sulfate and bismuth trioxide; the rare earth ion source is one or more of rare earth ion nitrate, rare earth ion chloride and rare earth ion oxide; the rare earth ions are one or more of Yb, er, tm, ho.
Further, the bromine source is one or more of sodium bromide, potassium bromide, calcium bromide, ammonium bromide and cetyltrimethylammonium bromide; the concentration of the aqueous solution containing the bromine source is 0.5-5M.
Further, in the bismuth source, the rare earth ion source and the bromine source described in Step1, the molar ratio of Bi ion to rare earth ion to chloride ion=0.9: 0.1:1.
further, the hydrothermal reaction temperature in Step1 is 120-220 ℃, and the hydrothermal reaction time is 6-36 h.
Further, the molybdenum source in Step2 is one of ammonium molybdate or molybdenum acetylacetonate; the mass ratio of the BiOBr to the RE and the molybdenum source is 1:0.005-0.015.
Further, the annealing temperature in Step3 is 400-500 ℃, and the annealing is performed in an air atmosphere for 1-6 hours.
The beneficial effects of the invention are as follows:
MoO prepared by the invention 3-x The RE heterojunction photocatalyst has excellent catalytic degradation effect on antibiotics and organic dye pollutants, and has the advantages of high separation efficiency of photogenerated carriers, effective utilization of near infrared light and high catalytic efficiency; meanwhile, the material has the advantages of simple preparation method, mild reaction condition and low cost, is suitable for large-scale production, and is a novel and efficient material for photocatalytic degradation of antibiotic pollutants.
Drawings
In order to more clearly illustrate the technical solutions of the embodiments of the present invention, the drawings that are needed for the description of the embodiments will be briefly described below, and it is obvious that the drawings in the following description are only some embodiments of the present invention, and that other drawings may be obtained according to these drawings without inventive effort for a person skilled in the art.
FIG. 1 shows MoO prepared in examples 1-3 and comparative example 1 3-x /BiOBr:Yb 3+ ,Er 3+ X-ray diffraction pattern of heterojunction photocatalyst;
FIG. 2 shows MoO prepared in examples 1-3 and comparative example 1 3-x /BiOBr:Yb 3+ ,Er 3+ An ultraviolet-visible-near infrared absorption spectrum of the heterojunction photocatalyst;
FIG. 3 shows MoO prepared in examples 1-3 and comparative example 1 3-x /BiOBr:Yb 3+ ,Er 3+ Performance profile of heterojunction photocatalyst for photocatalytic degradation of BPA.
Detailed Description
The following description of the embodiments of the present invention will be made clearly and completely with reference to the accompanying drawings, in which it is apparent that the embodiments described are only some embodiments of the present invention, but not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
Example 1
MoO (MoO) 3-x /BiOBr:Yb 3+ ,Er 3+ Heterojunction photocatalystThe preparation method of (2) comprises the following steps:
(1) 2 to 5mol of bismuth nitrate pentahydrate, 0.2 to 0.5mL of aqueous solution of erbium nitrate (0.1M) and 0.08 to 0.2mL of aqueous solution of ytterbium nitrate (0.5M) are added into 30mL of aqueous solution of mannitol (0.1M), and after the solution is stirred until the solution is transparent, 0.8 to 2mL of solution of potassium bromide with the concentration of 2.5M is added, and the mixed solution is obtained after full stirring. Transferring the mixed solution into a polytetrafluoroethylene reaction kettle, carrying out hydrothermal reaction at 160 ℃ for 12 hours, and naturally cooling to room temperature after the reaction is completed to obtain a precipitate.
(2) Centrifuging and washing the precipitate obtained in the step (1) by using ionized water and ethanol respectively, and drying at 70 ℃ to obtain BiOBr:Yb 3+ ,Er 3+ A precursor.
(3) BiOBr: yb 3+ ,Er 3+ And (NH) 4 ) 2 MoO 4 Mixing according to the mass ratio of 1:0.015, fully grinding, transferring into a crucible, annealing at 450 ℃ for 2 hours, and naturally cooling to room temperature after the reaction is completed to obtain MoO 3-x /BiOBr:Yb 3+ ,Er 3+ Heterojunction photocatalyst, labeled BYE-1.5% MoO 3-x 。
Example 2
MoO (MoO) 3-x /BiOBr:Yb 3+ ,Er 3+ The preparation method of the heterojunction photocatalyst comprises the following steps:
(1) 2 to 5mol of bismuth sulfate, 0.2 to 0.5mL of aqueous solution of erbium nitrate (0.1M) and 0.08 to 0.2mL of aqueous solution of ytterbium nitrate (0.5M) are added into 30mL of aqueous solution of mannitol (0.1M), and after the solution is stirred until transparent, 0.8 to 2mL of solution of sodium bromide with the concentration of 2.5M is added, and the mixed solution is obtained after full stirring. Transferring the mixed solution into a polytetrafluoroethylene reaction kettle, carrying out hydrothermal reaction at 160 ℃ for 12 hours, and naturally cooling to room temperature after the reaction is completed to obtain a precipitate.
(2) Centrifuging and washing the precipitate obtained in the step (1) by using ionized water and ethanol respectively, and drying at 70 ℃ to obtain BiOBr:Yb 3+ ,Er 3+ A precursor.
(3) BiOBr: yb 3+ ,Er 3+ And (NH) 4 ) 2 MoO 4 Mixing according to the mass ratio of 1:0.01, fully grinding, transferring into a crucible, annealing at 450 ℃ for 2 hours, and naturally cooling to room temperature after the reaction is completed to obtain MoO 3-x /BiOBr:Yb 3+ ,Er 3+ Heterojunction photocatalyst, labeled BYE-1% MoO 3-x 。
Example 3
MoO (MoO) 3-x /BiOBr:Yb 3+ ,Er 3+ The preparation method of the heterojunction photocatalyst comprises the following steps:
(1) 2 to 5mol of bismuth nitrate pentahydrate, 0.2 to 0.5mL of aqueous solution of erbium nitrate (0.1M) and 0.08 to 0.2mL of aqueous solution of ytterbium nitrate (0.5M) are added into 30mL of aqueous solution of mannitol (0.1M), and after the solution is stirred until transparent, 0.8 to 2mL of solution of sodium bromide with the concentration of 2.5M is added, and after the solution is fully stirred, a mixed solution is obtained. Transferring the mixed solution into a polytetrafluoroethylene reaction kettle, carrying out hydrothermal reaction at 160 ℃ for 12 hours, and naturally cooling to room temperature after the reaction is completed to obtain a precipitate.
(2) Centrifuging and washing the precipitate obtained in the step (1) by using ionized water and ethanol respectively, and drying at 70 ℃ to obtain BiOBr:Yb 3+ ,Er 3+ A precursor.
(3) BiOBr: yb 3+ ,Er 3+ And (NH) 4 ) 2 MoO 4 Mixing according to the mass ratio of 1:0.005, fully grinding, transferring into a crucible, annealing at 450 ℃ for 2 hours, and naturally cooling to room temperature after the reaction is completed to obtain MoO 3-x /BiOBr:Yb 3+ ,Er 3+ Heterojunction photocatalyst, labeled BYE-0.5% MoO 3-x 。
Example 4
MoO (MoO) 3-x /BiOBr:Yb 3+ ,Tm 3+ The preparation method of the heterojunction photocatalyst comprises the following steps:
(1) 2 to 5mol of bismuth sulfate, 0.2 to 0.5mL of thulium nitrate aqueous solution (0.1M) and 0.08 to 0.2mL of ytterbium nitrate aqueous solution (0.5M) are added into 30mL of mannitol aqueous solution (0.1M), and after the solution is stirred until transparent, 0.8 to 2mL of potassium bromide solution with the concentration of 2.5M is added, and the mixed solution is obtained after full stirring. Transferring the mixed solution into a polytetrafluoroethylene reaction kettle, carrying out hydrothermal reaction at 160 ℃ for 12 hours, and naturally cooling to room temperature after the reaction is completed to obtain a precipitate.
(2) Centrifuging and washing the precipitate obtained in the step (1) by using ionized water and ethanol respectively, and drying at 70 ℃ to obtain BiOBr:Yb 3+ ,Er 3+ A precursor.
(3) BiOBr: yb 3+ ,Tm 3+ And (NH) 4 ) 2 MoO 4 Mixing according to the mass ratio of 1:0.015, fully grinding, transferring into a crucible, annealing at 450 ℃ for 2 hours, and naturally cooling to room temperature after the reaction is completed to obtain MoO 3-x /BiOBr:Yb 3+ ,Tm 3+ Heterojunction photocatalyst, labeled BYT-1.5% MoO 3-x 。
Example 5
MoO (MoO) 3-x /BiOBr:Yb 3+ ,Er 3+ ,Ho 3+ The preparation method of the heterojunction photocatalyst comprises the following steps:
(1) 2 to 5mol of bismuth nitrate pentahydrate, 0.1 to 0.25mL of holmium nitrate aqueous solution (0.1M), 0.1 to 0.25mL of erbium nitrate aqueous solution and 0.08 to 0.2mL of ytterbium nitrate aqueous solution (0.5M) are added into 30mL of mannitol aqueous solution (0.1M), and after the solution is stirred until transparent, 0.8 to 2mL of potassium bromide solution with the concentration of 2.5M is added, and after the solution is fully stirred, a mixed solution is obtained. Transferring the mixed solution into a polytetrafluoroethylene reaction kettle, carrying out hydrothermal reaction at 160 ℃ for 12 hours, and naturally cooling to room temperature after the reaction is completed to obtain a precipitate.
(2) Centrifuging and washing the precipitate obtained in the step (1) by using ionized water and ethanol respectively, and drying at 70 ℃ to obtain BiOBr:Yb 3+ ,Er 3+ ,Ho 3+ A precursor.
(3) BiOBr: yb 3+ ,Er 3+ ,Ho 3+ And (NH) 4 ) 2 MoO 4 Mixing according to the mass ratio of 1:0.015, fully grinding, transferring into a crucible, annealing at 450 ℃ for 2 hours, and naturally cooling to room temperature after the reaction is completed to obtain MoO 3-x /BiOBr:Yb 3+ ,Er 3+ ,Ho 3+ Heterojunction photocatalyst, labeled BYEH-1.5% MoO 3-x 。
Example 6
MoO (MoO) 3-x /BiOBr:Er 3+ The preparation method of the heterojunction photocatalyst comprises the following steps:
(1) 2-5 mol of bismuth nitrate pentahydrate and 5mL of erbium nitrate aqueous solution (0.1M) are added into 25mL of mannitol aqueous solution (0.1M), and after the solution is stirred until transparent, 0.8-2mL of potassium bromide solution with the concentration of 2.5M is added, and after the solution is fully stirred, a mixed solution is obtained. Transferring the mixed solution into a polytetrafluoroethylene reaction kettle, carrying out hydrothermal reaction at 160 ℃ for 12 hours, and naturally cooling to room temperature after the reaction is completed to obtain a precipitate.
(2) Centrifuging and washing the precipitate obtained in the step (1) by using ion water and ethanol respectively, and drying at 70 ℃ to obtain BiOBr:Er 3+ A precursor.
(3) BiOBr: er 3+ And (NH) 4 ) 2 MoO 4 Mixing according to the mass ratio of 1:0.015, fully grinding, transferring into a crucible, annealing at 450 ℃ for 2 hours, and naturally cooling to room temperature after the reaction is completed to obtain MoO 3-x /BiOBr:Er 3+ Heterojunction photocatalyst, labeled BE-1.5% MoO 3-x 。
Comparative example 1
MoO (MoO) 3-x /BiOBr:Yb 3+ ,Er 3+ The preparation method of the heterojunction photocatalyst comprises the following steps:
(1) 2-5 mol of bismuth nitrate pentahydrate, 0.2-0.5 mL of erbium nitrate aqueous solution (0.1M) and 0.08-0.2 mL of ytterbium nitrate aqueous solution (0.5M) are added into 30mL of mannitol aqueous solution (0.1M), and after stirring until the solution is transparent, 0.8-2mL of potassium bromide solution with the concentration of 2.5M is added, and after full stirring, the mixed solution is obtained. Transferring the mixed solution into a polytetrafluoroethylene reaction kettle, carrying out hydrothermal reaction at 160 ℃ for 12 hours, and naturally cooling to room temperature after the reaction is completed to obtain a precipitate.
(2) Centrifuging and washing the precipitate obtained in the step (1) by using ionized water and ethanol respectively, and drying at 70 ℃ to obtain BiOBr:Yb 3+ ,Er 3+ A photocatalyst. In comparison with example 1, the catalyst was not identical to (NH) 4 ) 2 MoO 4 Reaction shapeAnd the heterojunction is formed, and the photocatalytic performance is poor.
Comparative example 2
MoO (MoO) 3-x /BiOBr:Yb 3+ ,Er 3+ The preparation method of the heterojunction photocatalyst comprises the following steps:
(1) 2 to 5mol of bismuth nitrate pentahydrate, 0.2 to 0.5mL of aqueous solution of erbium nitrate (0.1M) and 0.08 to 0.2mL of aqueous solution of ytterbium nitrate (0.5M) are added into 30mL of aqueous solution of mannitol (0.1M), and after the solution is stirred until the solution is transparent, 0.8 to 2mL of solution of potassium bromide with the concentration of 2.5M is added, and the mixed solution is obtained after full stirring. Transferring the mixed solution into a polytetrafluoroethylene reaction kettle, carrying out hydrothermal reaction at 160 ℃ for 12 hours, and naturally cooling to room temperature after the reaction is completed to obtain a precipitate.
(2) Centrifuging and washing the precipitate obtained in the step (1) by using ionized water and ethanol respectively, and drying at 70 ℃ to obtain BiOBr:Yb 3+ ,Er 3+ A precursor.
(3) BiOBr: yb 3+ ,Er 3+ And (NH) 4 ) 2 MoO 4 Mixing according to the mass ratio of 1:0.015, fully grinding, transferring into a crucible, annealing at 300 ℃ for 2 hours, and naturally cooling to room temperature after the reaction is completed to obtain MoO 3-x /BiOBr:Yb 3+ ,Er 3+ Heterojunction photocatalyst, labeled BYE-1.5% MoO 3-x . Compared with example 1, the annealing temperature is low, so MoO is not formed 3-x /BiOBr:Yb 3+ ,Er 3+ Heterojunction photocatalyst with lower catalytic performance
As can be seen from comparative example 1, moO 3-x /BiOBr:Yb 3+ ,Er 3+ The formation of heterojunction can obviously improve the charge separation and transfer efficiency between semiconductor heterojunction, and greatly improve the BiOBr: yb 3+ ,Er 3+ Is used for the photocatalytic performance of the catalyst. As is clear from comparative example 2. The shortened annealing time results in (NH) 4 ) 2 MoO 4 Insufficient reaction, failure to react with BiOBr: yb 3+ ,Er 3+ And a heterostructure is formed, so that the photocatalytic and luminous performances of the solar cell are reduced. MoO as shown in figures 2 and 3 3-x /BiOBr:Yb 3+ ,Er 3+ Heterojunction significantly enhances BiOBr: yb 3+ ,Er 3+ The photocatalytic performance of the solar energy collector can generate stronger light absorption in the visible-near infrared region of 400-1400 nm, and the solar energy utilization rate is greatly improved.
Claims (8)
1. The molybdenum oxide/bismuth oxybromide composite photocatalyst is characterized in that the chemical formula of the catalyst is as follows: moO (MoO) 3-x /BiOBr:RE。
2. The method for preparing the molybdenum oxide/bismuth oxybromide composite photocatalyst according to claim 1, comprising the following steps:
step1: dissolving a bismuth source and a rare earth ion source in a mannitol solvent, stirring and mixing uniformly, adding an aqueous solution containing a bromine source, performing hydrothermal reaction on the obtained aqueous solution, centrifuging, washing and drying to obtain a BiOBr: RE precursor;
step2: adjusting the proportion of BiOBr, RE and a molybdenum source, and fully grinding and stirring;
step3: annealing the mixture obtained in Step2 to obtain MoO 3-x BiOBr: RE composite photocatalyst.
3. The method for preparing the molybdenum oxide/bismuth oxybromide composite photocatalyst according to claim 2, which is characterized in that: the volume ratio of the bismuth source to the mannitol solution is 0.1-3 g:20-50 mL; the bismuth source is one or more of bismuth nitrate pentahydrate, bismuth carbonate, bismuth phosphate, bismuth sulfate and bismuth trioxide; the rare earth ion source is one or more of rare earth ion nitrate, rare earth ion chloride and rare earth ion oxide; the rare earth ions are one or more of Yb, er, tm, ho.
4. The method for preparing the molybdenum oxide/bismuth oxybromide composite photocatalyst according to claim 2, which is characterized in that: the bromine source is one or more of sodium bromide, potassium bromide, calcium bromide, ammonium bromide and cetyltrimethylammonium bromide; the concentration of the aqueous solution containing the bromine source is 0.5-5M.
5. The method for preparing the molybdenum oxide/bismuth oxybromide composite photocatalyst according to claim 2, which is characterized in that: in the bismuth source, the rare earth ion source and the bromine source described in Step1, the molar ratio of Bi ion to rare earth ion to chloride ion=0.9: 0.1:1.
6. the method for preparing the molybdenum oxide/bismuth oxybromide composite photocatalyst according to claim 2, which is characterized in that: the hydrothermal reaction temperature in Step1 is 120-220 ℃, and the hydrothermal reaction time is 6-36 h.
7. The method for preparing the molybdenum oxide/bismuth oxybromide composite photocatalyst according to claim 2, which is characterized in that: the molybdenum source in Step2 is one of ammonium molybdate or molybdenum acetylacetonate; the mass ratio of the BiOBr to the RE and the molybdenum source is 1:0.005-0.015.
8. The method for preparing the molybdenum oxide/bismuth oxybromide composite photocatalyst according to claim 2, which is characterized in that: the annealing temperature in Step3 is 400-500 ℃, and the annealing is carried out in air atmosphere for 1-6 h.
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